Molecular Complexity in Modern Chemistry MCMC-2014 BOOK OF ABSTRACTS September 13-19, 2014 Moscow, Russia

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1 RUSSIA ACADEMY F SCIECES (RAS) DIVISI F CHEMISTRY AD MATERIAL SCIECES, RAS RUSSIA FUDATI FR BASIC RESEARCH SCIETIFIC CUCIL RGAIC CHEMISTRY, RAS D ZELISKY ISTITUTE F RGAIC CHEMISTRY, RAS International Conference Molecular Complexity in Modern Chemistry MCMC-2014 BK F ABSTRACTS September 13-19, 2014 Moscow, Russia

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3 International Advisory Committee H. Alper, University of ttawa, Canada D. Astruc, University of Bordeaux, France J. Dupont, Institute of Chemistry, Brazil P. J. Dyson, EPFL, Switzerland R. G. Finke, Colorado State University, USA G. C. Fu, California Institute of Technology, USA A. Furstner, Max Planck Institut fur Kohlenforschung, Germany V. K. Jain, Bhabha Research Centre, India C.W. Jones, Georgia Institute of Technology, USA P.-H. Leung, anyang Technological University, Singapore C. ajera, Universidad de Alicante, Spain E.-i. egishi, Purdue University, USA L. A. ro, University of Zaragoza-CSIC, Spain R. Poli, Institut ational Polytechnique, France V. Snieckus, Queen's University, Canada M. Taillefer, Institut Charles Gerhardt, France A. M. Trzeciak, University of Wroclaw, Poland Y. Yamamoto, Tohoku University, Japan

4 Local rganizing Committee D Zelinsky Institute of rganic Chemistry, RAS M. P. Egorov, Chairman V. P. Ananikov, Vice-chairman A. D. Dilman A. M. Sakharov A. Y. Stakheev A.M. Starosotnikov A.. Terentev. V. Turova S. G. Zlotin ational Advisory Committee G. A. Abakumov,. ovgorod I. P. Beletskaya, Moscow Y.. Bubnov, Moscow V.. Charushin, Ekaterinburg.. Chupakhin, Ekaterinburg A. I. Konovalov, Kazan V. V. Lunin, Moscow V. I. Minkin, Rostov. M. efedov, Moscow V.. Parmon, ovosibirsk. G. Syniashin, Kazan V. A. Tartakovsky, Moscow B. A. Trofimov, Irkutsk M. S. Yunusov, Ufa. S. Zefirov, Moscow

5 Index Plenary Lectures... 7 Invited Lectures ral Communications Posters Authors Index

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7 Plenary Lectures 7

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9 PL1 THE APPLICATI F PHTREDX CATALYSIS T EW TRASFRMATIS I CHEMICAL SYTHESIS D.W.C. MacMillan Merck Center for Catalysis, Princeton University,Princeton, J This lecture will discuss the advent and development of new concepts in chemical synthesis, specifically the combination of photoredox catalysis with organic catalysis. This new approach to synergistic catalysis will demonstrate that multiple yet separate catalytic cycles can be aligned to generate activated intermediates that rapidly combine with each other, thereby allowing new approaches to enantioselective C C and C-heteroatom bond formation. We will also introduce an approach to the discovery of new chemical reactions that we term accelerated serendipity. Accidental or serendipitous discoveries have led to some of the most important breakthroughs in scientific history, many of which have directly affected human life. Given our overarching goal of developing fundamentally new and useful chemical transformations using catalysis and by acknowledging the tremendous impact of serendipity in scientific discovery, we questioned whether this phenomenon could be forced or simulated and therefore employed as a tool for reaction discovery. In this presentation, we will describe several new transformations that have been discovered via accelerated serendipity that we expect will find widespread adoption throughout the field of chemical synthesis. Moreover, we will further describe how mechanistic understanding of these processes has led to the design of a valuable, new yet fundamental chemical transformation. Acknowledgements Financial support was provided by IHGMS (R01 01 GM ) and kind gifts from Merck, Amgen, and Abbott. 9

10 PL2 GLD CATALYSIS 2.0 A.S.K. Hashmi rganisch-chemisches Institut, Fakultät für Chemie und Geowissenschaften, Universität Heidelberg, Im euenheimer Feld 270, Heidelberg, Germany Homogeneous catalysis by gold has developed to an important sector of catalysis research. 1 Initially, efforts in methodology development clearly dominated, in the last years also an increasing number of applications in synthesis has been reported. 2,3 Efforts to understand the basic mechanism of these reactions continuously accompanied the field. 4 For twelve years most of the reactions followed simple reaction mechanisms basing on the interaction of one gold centre in a gold complex or organogold compound with the substrate molecule. In most of these reactions vinylgold or alkylgold intermediates are involved, sometimes also gold carbenoids. ow an entirely new family of reactions, basing on the activation of the organic substrates by two gold complexes at the same time (one -coordinated, the other -coordinated), has been discovered. These open up entirely new synthetic possibilities and follow quite complex mechanisms. These mechanisms, which are new to the field of organometallic chemistry, will be discussed in detail. Some of the new reactions even allow positional selective C,H activations of alkyl side chains, as exemplified below. The presentation will also contain results from computational chemistry. References: 1. A. S. K. Hashmi, Chem. Rev. 2007, 107, A. S. K. Hashmi, M. Rudolph, Chem. Soc. Rev. 2008, 37, M. Rudolph, A. S. K. Hashmi, Chem. Soc. Rev. 2012, 41, A. S. K. Hashmi, Angew. Chem. Int. Ed. 2010, 49,

11 PL3 HW MUCH CATALYST D WE EED? C. Bolm Institute of rganic Chemistry, RWTH Aachen University, Aachen, Germany Various C--, C--, and C-C-bond forming reactions leading to cross coupling-type products can be performed without transition metals. In this presentation we will discuss cyclizations affording benzimidazol-2-ones 1 and indazoles 2 (eqs. 1 and 2, respectively). Photochemical initiations (eq. 3) led us to other directions. 3,4 R 1 R 2 X R 2 H R 3 KH/DMS 40 C, 24 h X = I, Br (Cl, F) R 1 R 2 R 3 R 2 (eq. 1) R 1 X H R 3 diamine/k 2 C 3 toluene, RT, 2.5 h X = I, Br R1 R 3 TMS (eq. 2) R 1 TMS R 2 hn CH 2 Cl 2, RT R 1 R 2 (eq. 3) Finally we will present mechanochemical activations in ball mills that allow reducing the catalyst loadings in asymmetric organocatalyses. 5-7 References: 1. a) Yuan, Y.; Thomé, I.; Kim, S. H.; Chen, D.; Beyer, A.; Bonnamour, J.; Zuidema, E.; Chang, S.; Bolm, C. Adv. Synth. Catal. 2010, 352, b) Beyer, A.; Reucher, C. M. M.; Bolm, C. rg. Lett. 2011, 13, c) Thomé, I.; Bolm, C. rg. Lett. 2012, 14, d) Beyer, A.; Buendia, J.; Bolm, C. rg. Lett. 2012, 14, e) Baars, H.; Beyer, A.: Kohlhepp, S. V.; Bolm, C. rg. Lett. 2014, 16, Thomé, I.; Besson, C.; Kleine, T.; Bolm, C. Angew. Chem. Int. Ed. 2013, 52, a) Zhang, H.-J.; Becker, P. Huang, H.; Pirwerdjan, R.; Pan, F.-F.; Bolm, C. Adv. Synth. Catal. 2012, 354, b) Becker, P.; Priebbenow, D. L.; Zhang, H.-J.; Pirwerdjan, R.; Bolm, C. J. rg. Chem. 2014, 79, 814. c) Becker, P.; Priebbenow, D. L.; Pirwerdjan, R.; Bolm, C. Angew. Chem. Int. Ed. 2014, 53, For a photochemical activation in a metal catalysis, see: Bizet, V.; Buglioni, L.; Bolm, C. Angew. Chem. Int. Ed. DI: /anie a) Jörres, M.; Mersmann, S.; Raabe, G.; Bolm, C. Green Chem. 2013, 15, 612. See also in: b) Kleine, T.; Buendia, J.; Bolm, C. Green Chem. 2013, 15, For a video, see: 7. For a general overview, see: James, S. L.; Collier, P.; Parkin, I.; Hyett, G.; Braga, D.; Maini, L.; Jones, B.; Friscic, T.; Bolm, C.; Krebs, A.; Mack, J.; Waddell, D. C.; Shearouse, W. C.; rpen, G.; Adams,C.; Steed, J. W.; Harris, K. D. M. Chem. Soc. Rev. 2012, 41,

12 PL4 MLECULAR METATHESIS CATALYSTS AT THE DAW F IDUSTRIAL IMPLEMETATI D.E. Fogg University of ttawa Ruthenium-catalyzed olefin metathesis has enormous potential for impact on the chemical enterprise, in sectors ranging from pharma to specialty polymers and green feedstocks. Phosphine-free metathesis catalysts, particularly those of the Hoveyda type (HII, see Figure 1), occupy a position of increasing prominence. In one of the most high-profile current applications of metathesis chemistry, transformation of seed oils into functionalized olefins, HII significantly outperforms the benchmark Grubbs catalyst GII, [1,2] despite the fact that the two catalysts generate a common active species (A). Reports from pharma R&D indicate that HII also offers superior performance in some demanding RCM applications (RCM = ring-closing metathesis). [3] As these and closely related molecular metathesis catalysts enter deployment in process chemistry, understanding the mechanistic basis of their performance takes on added importance. We will discuss potential contributors to the improved productivity of HII: the absence of free PCy 3, the presence of the styrenyl ether ligand, and operation of HII via interchange-associative pathways. The relevance of each of these factors will be considered in the context of demanding ring-closing and cross-metathesis reactions.. Figure 1. Molecular structure of an organometallic product. References [1] Miao, X.; Fischmeister, C.; Dixneuf, P. H.; Bruneau, C.; Dubois, J. L.; Couturier, J. L. Green Chem. 2012, 14, [2] Biermann, U.; Bornscheuer, U.; Meier, M. A. R.; Metzger, J..; Schafer, H. J. Angew. Chem. Int. Ed. 2011, 50, [3] van Lierop, B. J.; Lummiss, J. A. M.; Fogg, D. E., Ring-Closing Metathesis: A How-To Guide. In lefin Metathesis: Theory and Practice, Grela, K., Ed. Wiley: Weinheim,

13 PL5 REDUCTIS WITH RGAIC REAGETS THE ELECTR AS A CATALYST! A. Studer WWU Muenster, Chemistry, Germany In the lecture reduction processes for generation of various radicals using different organic reagents will be presented. Reactions are generally conducted using stoichiometric SET-reagents. However, also some catalytic variants will be presented. In the presentation radical perfluoroalkylations and azidations will be addressed. Moreover, the concept of using the electron as a catalyst will be discussed and some examples provided. 13

14 PL6 AELECTRICS: MLECULAR METAL WIRES AD RELATED MLECULAR MATERIALS S.M. Peng Department of Chemistry, ational Taiwan University, Taipei, Taiwan We have designed a series of new ligands such as oligo-α-pyridylamines, and used them to construct an unique class of quadruple helix of metal strings. This achievement leads to a new direction to the application of molecular wires in the nanoelectronics. The outline is as follows: I. Linear Metal String Complexes (1) Synthesis, Structure, Bonding II. Potential Application as Molecular Metal Wires & Molecular Switches (2) STM-bj Study on the Conductivity of Metal Strings Comparative Study on the I-V Characterisics (Theory V.S. Experiment) III. Tuning of the Metal Strings (3-9) aphthyridyl Amino Ligands: Low xidation Mixed Metal Strings Asymmetrical Ligands: Toward Molecular Rectifier Heteronuclear Metal String Complexes Chiral Quadruple Helixes IV. Conclusion X M M M M M m Fig.1 Metal Strings of ligo- -pyridylamido Ligands 1. C.-Y. Yeh, C.-C. Wang, Y.-H. Chen and S.-M. Peng, in Redox Systems Under ano-space Control, Ed: T, Hirao, Springer, Germany 2006, Ch I.-W. P. Chen, M.-D. Fu, W.-H. Tseng, J.-Y. Yu, S.-H. Wu, C.-J. Ku, C.-H. Chen, and S.-M. Peng, Angew. Chem. Int. Ed. Engl. 2006, (a) C.-H. Chien, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang and S.-M. Peng, Dalton Trans. 2006, (b) C.-H. Chien, G.-H. Lee, Y. Song and S.-M. Peng, Dalton Trans. 2006, M.-M. Rohmer, I. P.-C. Liu, J.-C. Lin, M.-J. Chiu, C.-H. Lee, G.-H. Lee, M. Benard, X. Lopez, S.-M. Peng, Angew. Chem. Int. Ed. Engl. 2007, 46, I. P.-C. Li, W.-Z. Wang, and S.-M. Peng, Chem. Commun. 2009, R. H. Ismayilov, W.-Z.Wang, G. H. Lee, C. Y. Yeh, S. A. Hua, Y. Song, M. M. Rohmer, M. Bénard, S.-M. Peng, Angew. Chem. Int. Ed., 2011, 50, I. P.-C. Liu, C.-H. Chen, S.-M. Peng, Bull. Jpn. Soc. Coord. Chem., 2012, 59, X M = i, C o, C r m = 0, 1, 2, 3 X = C l, C S 14

15 8. M.-C. Cheng, C.-L. Mai, C.-Y. Yeh, G.-H. Lee, S.-M. Peng, Chem. Commun. 2013, 49, M.-J. Huang, S.-A Hua, M.-D. Fu, G.-C. Huang, C. Yin, C.-H. Ko, C-K. Kuo, C-H. Hsu, G.-H. Lee, K.-Y. Ho, C.-H. Wang, Y.-W. Yang, I.-C Chen, S.-M. Peng, C.-h. Chen, Chem. Eur. J. 2014, DI: /chem

16 PL7 EW CYCLADDITI STRATEGIES BASED STRAIED AD UUSUAL MLECULES R.L. Danheiser Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA USA Highly substituted carbocyclic and heterocyclic rings are key structural features in many biologically significant and commercially important compounds. Although classical synthetic approaches to such compounds have generally relied on linear substitution strategies, convergent cycloaddition and annulation strategies have emerged as powerful alternative methods for the assembly of highly substituted cyclic compounds. The intrinsic convergent nature of cycloaddition and annulation strategies facilitates the efficient assembly of highly substituted systems that would have required long, multistep routes using alternative methods. This talk will focus on the application of strained and unusual molecules as building blocks in cycloaddition strategies for the construction of complex carbocyclic and heterocyclic compounds. The synthetic utility of highly unsaturated, conjugated molecules such as vinylketenes, conjugated enynes, vinylallenes, allenylimines, and iminoacetonitriles will be described, as well as their application in the total synthesis of natural products. 16

17 PL8 SILIC TETHER MTIF I C-H ACTIVATI REACTIS V. Gevorgyan University of Illinois at Chicago We have developed a set of new transition metal-catalyzed C-H activation methodologies employing a silicon-tether motif. These methods feature: (a) use of silyl group as a tether between a substrate and a reagent, thus transforming intermolecular reaction into intramolecular reaction; 1-2 (b) employment of a silicon-tethered directing group, which is traceless or easily convertable into valuable functionalities; 3-8 (c) use of silyl-tethered hydrosilane reagent; 9-10 and (d) introduction of new /Si-chelation concept that allows for a remote activation of aliphatic C-H bonds. 11 The scope of these transformations will be demonstrated and the mechanisms will be discussed. References 1. Huang C., Gevorgyan V. J. Am. Chem. Soc. 2009, 131, Huang, C.; Gevorgyan, V. rg. Lett. 2010, 12, Chernyak., Dudnik A. S., Huang C., Gevorgyan V. J. Am. Chem. Soc. 2010, 132, Dudnik A. S., Chernyak., Huang C., Gevorgyan V. Angew. Chem., Int. Ed. 2010, 49, Huang C., Chattopadhyay B., Gevorgyan V. J. Am. Chem. Soc. 2011, 133, Huang C., Ghavtadze., Chattopadhyay B., Gevorgyan V. J. Am. Chem. Soc. 2011, 133, Gulevich, A. V.; Melkonyan, F. S.; Sarkar, D.; Gevorgyan, V. J. Am. Chem. Soc. 2012, 134, Sarkar, D.; Melkonyan, F. S.; Gulevich, A. V.; Gevorgyan, V. Angew. Chem., Int. Ed. 2013, 52, Kuznetsov, A.; Gevorgyan, V. rg. Lett. 2012, 14, Kuznetsov, A.; nishi, Y.; Inamoto, Y.; Gevorgyan, V. rg. Lett. 2013, 15, Ghavtadze, ; Melkonyan, F. S.; Gulevich, A.; Huang, C.; Gevorgyan, V. at. Chem. 2014, 6,

18 PL9 WERER CMPLEXES: A EW CLASS F CHIRAL HYDRGE BD DR CATALYSTS FR EATISELECTIVE RGAIC REACTIS J.A. Gladysz Department of Chemistry, Texas A&M University, P Box 30012, College Station, Texas , USA Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en) 3 ] 3+, and related species, have played important historical roles in the development of inorganic chemistry and stereochemistry. 1,2 As Werner described in 1912, the two enantiomers, commonly designated and, can be separated by crystallization of the diastereomeric tartrate salts. 2 However, despite the low cost and ready availability of the building blocks, there have been no applications in enantioselective organic synthesis. L H 2 H 2 H 2 Co 3+ H 2 H 2 H2 We have found that [Co(en) 3 ] 3+ and related cations can be rendered soluble in organic solvents by using lipophilic anions such as "BAr f ". 3 Suitably functionalized derivatives act as highly enantioselective catalysts for a variety of carbon-carbon bond forming reactions. The mechanisms involve outer sphere activation of the electrophile by hydrogen bonding to the H moieties. ther types of metal-containing chiral hydrogen bond donors are also effective, including a chelate of the CpRuL fragment. Ph Ph H 2 H 2 Time (h) Ph Ph X H 2 Co 3+ H 2 H 2 H2 Conversion (%) 2 Me Ph 2Cl BAr f Ph ee (%) 1.2 eq. Ph Ph H 2 H 2 H 2 H 2 Co 3+ H 2 H 2 Me Ph H 2 D H 2 10 mol% cat. Et 3, acetone 0 C H 2 H Ph Co 2BF 4 BAr f Ph H2 H 2 Ph Me X Me 2 L L L Time (h) Conversion (%) ee (%) Ph Ph H 2 H 2 Ph H 2 H Ph Co 2PF 6 BAr f Ph H2 H 2 Ph Time (h) Conversion (%) ee (%) Me Me 2 15 > >99 86 Me Me >99 94 Ph 1 Kauffman, G. B. Coord. Chem. Rev. 1974, 12, Werner, A. Chem. Ber. 1911, 44, and 1912, 45, Ganzmann, C.; Gladysz, J. A. Chem. Eur. J. 2008, 14, Ghosh, S. K.; jeda, A. S.; Guerrero-Leal, J.; Bhuvanesh,.; Gladysz, J. A. Inorg. Chem. 2013, 52, Thomas, C.; Gladysz, J. A. ACS Catalysis 2014, 5,

19 PL10 CMPLEXITY I SIMPLICITY: THE PRTTYPE REACTIS F CARBEE AALGS M.P. Egorov Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, , Russia 19

20 PL11 SELECTIVELY ALKYLATED AD ARYLATED -HETERARMATICS VIA ACCEPTRLESS DEHYDRGEATIVE CDESATI (ADC) REACTIS R. Kempe Lehrstuhl Anorganische Chemie II (Catalyst Design),University of Bayreuth, Bavaria, Germany Dwindling reserves of crude oil and the resulting price increase of this and other fossil carbon sources combined with environmental concerns have resulted in a call for the use of alternative, preferably renewable, resources. Aside from fuel, ultimately a wide variety of chemical feedstocks are derived from fossil sources. Renewable lignocellulosic materials are indigestible and therefore not useful as food products and can be processed to give alcohols and polyols. These rather highly oxidized hydrocarbons differ drastically in their chemical nature from the cracking products of crude oil. Thus, there is a high demand for new reactions that utilize alcohols and convert them into key chemicals. Recently, our group developed a sustainable catalytic pyrrole synthesis.[1] Secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation of C and C C bonds. Two equivalents of hydrogen gas and two equivalents of water are eliminated in the course of the reaction (Acceptorless Dehydrogenative Condensation, ADC). Alcohols based entirely on renewable resources can be used as starting materials. The catalytic synthesis protocol tolerates a large variety of functional groups, which includes olefins, chlorides, bromides, organometallic moieties, amines and hydroxyl groups. Furthermore, we have developed a catalyst that operates efficiently under mild conditions. This methodology could also be used to synthesize selectively functionalized pyridines from alcohols.[2] In the talk, the development of alcohol re-functionalization reactions and the design of catalyst systems that mediate these reactions are discussed. [1] S. Michlik, R. Kempe, ature Chem. 2013, 5, 140. [2] S. Michlik, R. Kempe, Angew. Chem. Int. Ed., 2013, 52,

21 PL12 THE CATALYST TDAY: BIG BAG AD LIFE AFTER I.P. Beletskaya Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia anocatalysis and catalysis by Lewis and Broensted acids will be considered in the lecture. 21

22 Invited Lectures 22

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24 IL1 CYCLIZATIS F ALKYES: FRM STEREELECTRICS T CASCADE TRASFRMATIS I.V. Alabugin Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Fl ne of the simplest organic functional groups, the alkyne moiety, is also one a useful starting point for the design of cascade transformations which proceed through the formation of multiple C-C, C- H, C- and C- bonds. [1] In this talk, I will illustrate how the revised stereoelectronic rules for alkyne cyclizations [2] can be used for the bottom-up preparation of carbon nanostructures for molecular electronics (i.e., graphene nanoribbons). In our approach, alkyne chains of varying sizes, shapes and functionalities, are built in a modular fashion and zipped up into graphene substructures via controlled cascades of all-exo or all-endo cyclizations. [3] Even in the presence of multiple functionalities, alkyne cascades can be made chemoselective via kinetic self-sorting of the pool of equilibrating radicals. [4] Further synthetic opportunities are presented by fusion of cyclization cascades with self-terminating fragmentations that allow use of alkenes as synthetic equivalents of alkynes. [5] [1] Alabugin, I. V.; Gold, B. J. rg. Chem., 2013, 78, [2] Alabugin, I. V.; Gilmore, K.; Manoharan, M. J. Am. Chem. Soc. 2011, 133, Alabugin, I. V.; Gilmore, K. Chem. Commun., 2013, 49, [3] Byers, P. M.; Rashid, J. I.; Mohamed, R. K.; Alabugin, I. V. rg. Lett., 2012, 14, Byers, P.; J. Am. Chem. Soc. 2012, 134, [4] Mondal, S.; Mohamed, R. K.; Manoharan, M.; Phan, H.; Alabugin, I. V. rg. Lett., 2013, 15, [5] Mondal, S.; Gold, B.; Mohamed, R. K.; Alabugin, I. V. Chemistry Eur. Journal, 2014, in print. 24

25 IL2 ARTIFICIAL PHTSYTHESIS USIG TRASITI METAL CMPLEXES. Ishitani Department of Chemistry, Tokyo Institute of Technology, Japan Both the problems of the global warming and shortage of the fossil fuels have brought about great interest in photochemical utilization of C 2 with solar energy. Efficient photocatalysts for C 2 reduction must be necessary for development of such an important technology. We have developed novel types of photocatalytic systems using metal complexes and/or semiconductors as a photocatalyst. 1 In this presentation, I will focus on the architecture of two types of the photocatalysts using transition metal complexes: (1) A mixed photocatalytic system including a ring-shaped Re(I) multinuclear complex as a photosensitizer 2 (2) Ru(II)-Re(I) and Ru(II)-Re(I) supramolecular photocatalysts. 3 The efficiency of the former photocatalytic system has been highest in the reported C 2 -reduction photocatalysts ( = 82%), and the latter photocatalysts have been most robust (T > 3000). References 1. (a) Yui, T.; Tamaki, Y.; Sekizawa, K.; Ishitani,., Photocatalytic reduction of C 2 : from molecules to semiconductors. Top. Curr. Chem. 2011, 303, ; (b) Sekizawa, K; Maeda, K.; Domen, K.; Koike, K.; Ishitani,. J. Am. Chem. Soc. 2013, 135, Morimoto, T; ishiura, C.; Tanaka, M.; Rohacova, J.; akagawa, Y.; Funada, Y.; Koike, K.; Yamamoto, Y.; Shishido, S.; Kojima, T.; Saeki, T.; zeki, T.; Ishitani,. J. Am. Chem. Soc. 2013, 135, (a) Gholamkhass, B.; Mametsuka, H.; Koike, K.; Tanabe, T.; Furue, M.; Ishitani,. Inorg. Chem. 2005, 44, 2326; (b) Sato, S.; Koike, K.; Inoue, H.; Ishitani,. Photochem. Photobiol. Sci. 2007, 6, 454; (c) Koike, K.; aito, S.; Sato, S.; Tamaki, Y.; Ishitani,. J Photochem. Photobiol. A: Chem. 2009, 207, 109; (d) Tamaki, Y.; Watanabe, K.; Koike, K.; Inoue, H.; Morimoto, T.; Ishitani,. Faraday Discuss. 2012, 155, 115; (e) Tamaki, Y.; Morimoto, T.; Koike, K.; Ishitani,. Proc. atl. Acad. Sci. USA 2012, 109, (f) Tamaki, Y.; Koike, K.; Morimoto, T.; Ishitani,. J. Cat. 2013, 135, 22; (g) Tamaki, Y.; Koike, K.; Morimoto, T.; Yamazaki, Y.; Ishitani,. Inorg. Chem. 2013, 52,

26 IL3 A PARADIGM FR THE PRACTICAL AD ECMICAL FRMATI F CARB CARB AD CARB HETERATM BDS. RGACATALYTIC REDX CUPLED, TRASITI METAL CATALYZED DEHYDRATIVE BD CSTRUCTIS L.S. Liebeskind, M.G. Lindale Emory University, Department of Chemistry, Atlanta, Georgia USA The current world-wide focus on C-H functionalization is driven, in part, by the conceptual promise of atom-efficient, sustainable syntheses from readily available feedstocks. f equal conceptual value is the dehydrative formation of C C, C, and C bonds from common bioavailable hydroxylic reactants like carboxylic acids, alcohols, and phenols. Given the sustainable generation of hydroxylic feedstocks, dehydrative bond formations can impact all levels of synthesis (commodities, fine chemicals, biologicals), if they are efficient, economical, practical, and substrate general. And, they are uniquely poised to contribute to the search for the sustainable conversion of biomass to biofuels. This lecture describes a paradigm for the conversion of hydroxylic reactants to value-added C C, C, and C products based on a practical, organocatalytic redox-coupled, transition metal catalyzed dehydrative bond forming process. 26

27 IL4 CHEMICAL SYTHESIS USIG AMPHTERIC MLECULES A.K. Yudin University of Toronto ver the past seven years, my lab has been exploring the use of amphoteric molecules in chemical synthesis. What started as a curiosity-driven project, has turned into a sustained exploration of a virtually untouched segment of chemistry characterized by molecules with unusual combinations of functional groups. The multifunctional nature arising from forced orthogonality enables amphoteric molecules to participate in reactions of high atom- and step- economy, thereby enabling efficient syntheses characterized by minimal reliance on protecting groups. In this lecture, I will illuminate several classes of reagents developed in our lab. I will discuss the discovery of bench-stable aldehydes equipped with a C-B bond at the alpha position. These intriguing molecules have enabled the synthesis of a rich palette of other reagents that contain carbon-boron bonds at strategic positions. With the growing repertoire of boron-containing amphoteric molecules, we are in a good position to explore ideas that range from reaction discovery to the synthesis of boron-based biologically active compounds. I will also present the evolution of peptide macrocyclization technology driven by amphoteric aziridine aldehydes. As part of this study, we are attempting to understand the conformational preferences of peptide macrocycles. As a result, we are moving closer to our ultimate goal of rationalizing the behavior of a wide range of substrate classes in our cyclization reactions, as well as understanding cellular activity of macrocycles. I will conclude my talk with a discussion of our integrative macrocyclization approaches and will present recent results of our protein crystallization efforts. 27

28 IL5 EMERGET FUCTI FRM CMPLEX ADAPTIVE CATALYSTS V.V. Fokin The Scripps Research Institute, Department of Chemistry, La Jolla, California, USA and Moscow Institute of Physics and Technology, Dolgoprudny, Russia Exploiting the versatility of catalytic processes requires rigorous interrogation of the constantly changing environment of the catalyst. Detailed understanding of critical events affecting a catalyst, such as activation and deactivation, unproductive off-cycle pathways, and changes in the nature of dominant species are of critical importance. The seemingly formidable challenge of controlling the reactivity of complex catalytic systems that involve dynamic and rapidly equilibrating mixtures of intermediates may, in fact, be their advantage: well-defined (i.e. non-adaptable) catalysts are often inefficient when compatibility with many functional groups and conditions is the goal. Examples of investigation of such catalytic reactions will be illustrated by case studies of transition metal-catalyzed transformations of alkynes. Alkynes are among the most energetic hydrocarbons, and transition metals enable selective and controlled manipulation of the triple bond, revealing their unique reactivity: transformations of alkynes into heterocycles and into a variety of molecules with new carbon heteroatom bonds. These seemingly simple transformations involve an impressive variety of intermediates yet proceed with high selectivity and efficiency, maintaining their reactivity in most complex environments, such as the biological milieu of living organisms. 28

29 IL6 RAPID PHTASSISTED ACCESS T sp 3 -RICH PLYHETERCYCLIC SCAFFLDS.A. Mukhina,..B. Kumar, W.C. Cronk, W.J. Umstead, A.G. Kutateladze Department of Chemistry and Biochemistry, University of Denver, USA Photochemical reactions hold unparalleled promise for building prohibitively strained carbo and heterocyclic scaffolds, which offer expeditious access to difficult synthetic targets not accessible via ground state chemistry. Yet, photochemistry is underutilized by the synthetic community, which is especially true for Diversity riented Synthesis (DS). In this context we have been developing a new photoassisted synthetic methodology which will enhance synthetic chemistry toolbox and will be compatible with DS.1 This new photoassisted synthetic methodology allows for rapid access to topologically diverse polycyclic scaffolds decorated by various functional groups and carbo/heterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these novel core frameworks. Access to such topologically diverse scaffolds is realized via key photochemical steps and their combination with ground state reactions, most prominently via the recently discovered intramolecular cycloaddition reactions of azaxylylenes and quinomethanes photogenerated via excited state intramolecular proton transfer. Details of an experimental and theoretical mechanistic study to gain deeper understanding of underlying processes in the excited states will also be discussed. A typical example of rapid growth of complexity in a photoassisted synthesis of enantiopure conformationally locked ribofuranosylamines spiro-linked to oxazolidino-diketopiperazines via a straightforward assembly of a threonine-based photoprecursor, photochemical transformation, and a simple post-photochemical modification, is shown below. [1] (a) Mukhina,.A.; Kumar,..B.; Arisco, T.M.; Valiulin, R.A.; Metzel, G.A.; Kutateladze, A.G. Angew. Chem. Int. Ed., 2011, 50, (b) andurkar,.s.; Kumar,..B.; Mukhina,.A.; Kutateladze, A.G. ACS Combinatorial Sci., 2013, 15, (c) Kumar,..B.; Mukhina,.A.; Kutateladze, A.G. J. Am. Chem. Soc., 2013, 135, (d) Cronk, W.C.; Mukhina,.A.; Kutateladze, A.G. J. rg. Chem., 2014, 79,

30 IL7 TRASITI METAL CLUSTERS: UAVIDABLE CTAMIATS R IMPRTAT PLAYERS I SLUTI? V.P. Ananikov Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, , Russia; Department of Chemistry, Saint Petersburg State University, Stary Petergof, , Russia Application of transition metal catalysis in organic synthesis is an area of outstanding progress with prominent achievements in carbon-carbon cross-coupling, carbon-heteroatom bond formation, and atom-economic construction of organic molecules. Mechanistic studies have revealed two different frameworks for catalytic processes in solution depending on the nature of selected system and on the type of catalyst precursor used: single type metal species catalysis or multiple metal species catalysis [1]. The first type of systems is widely utilized and it is based on well-defined metal complex with strongly bound ligands. The catalyst precursor undergoes only partial or minor chemical modifications prior entering the catalytic cycle. In this model, the formation of other metal derivatives is not facilitated and the active core of the catalyst is preserved throughout the catalytic cycle. The second model can be considered as multiple metal species catalysis (in some cases - cocktail of catalysts) and involves a range of simultaneously present and dynamically interchangeable metalcontaining species, such as metal complexes, clusters and nanoparticles [2]. Such mechanistic picture may be expected when in situ generated catalysts are employed or upon usage of nanoparticles as catalysts precursors. It is of much interest to reveal the role of metal clusters in these catalytic systems. Formation of clusters was detected in many cases, although their role remains unclear. In some cases the presence of clusters was related to decomposition of the active form, while in the other cases the formation of dinuclear and polynuclear species is an important stage of catalyst evolution in solution. We have investigated soluble metal complexes and nanoparticles of Pd, i, Pt and Au for development of efficient catalytic systems for selective carbon-heteroatom and carbon-carbon bond formation in solution [3-5]. Homogeneous transition-metal-catalyzed reactions and heterogeneous nanoparticle-catalyzed reactions were considered, with a focus on metal species interconversions and nanoparticle contamination of homogeneous catalytic systems. References [1] Kashin A.S., Ananikov V. P., J. rg. Chem., 2013, 78, (doi: /jo402038p). [2] Ananikov V. P., Beletskaya I. P., rganometallics, 2012, 31, 1595 (doi: /om201120n). [3] Zalesskiy S. S., Sedykh A. E., Kashin A. S., Ananikov V. P., J. Am. Chem. Soc., 2013, 135, 3550 (doi: /ja311258e). [4] Ananikov V. P., rlov. V., Zalesskiy S. S., Beletskaya I. P., Khrustalev V.., Morokuma K., Musaev D. G., J. Am. Chem. Soc., 2012, 134, 6637 (doi: /ja210596w). [5] Kashin A. S., Ananikov V. P., Top. Catal., 2013, 56, 1246 (doi: /s ). 30

31 IL8 SIMPLE CPPER CATALYSTS FR C-C, C- AD C- BDS FRMATI F. Monnier Institut Charles Gerhardt (UMR 5253) ESCM, FRACE Since its renaissance in 2001, [1] the copper cross-coupling of nucleophiles with aryl halides has been increasingly studied. [2] In this account, we exposed our last contribution for the formation of C-C, [3] C- [4] and C- [5] bonds catalyzed by a cheap and simple combination of copper salts and -diketone ligands. 1. a) M. Taillefer, H.-J. Cristau, P. P. Cellier, J.-F.Spindler, Env. SAU and SAU ; patents Fr W (Pr. b. Fr ); M. Taillefer, H.-J. Cristau, P. P. Cellier, J.-F. Spindler, A. uali, Fr W (Pr. b. Fr ); b) S. L. Buchwald, A. Klapars, J. C. Antilla, G. E. Job, M. Wolter, F. Y. Kwong, G. ordmann, E. J. Hennessy,W02/ (priority number US , 2001) 2. For a review, see: F. Monnier, M. Taillefer Angew. Chem., Int. Ed. 2009, 48, a) G. Danoun, A. Tlili, F. Monnier, M. Taillefer Angew. Chem. Int. Ed., 2012, 51, b) M.Taillefer, F. Monnier, A. Tlili, G. Danoun. PCT Int. Appl. (2013), W 2013 EP ; FR a) A. Tlili, F. Monnier, M. Taillefer Chem. Commun., 2012, 48, b) E. Racine, F. Monnier, J.-P. Vors, M. Taillefer Chem. Commun., 2013, 49, c) E. Racine, F. Monnier, J.- P. Vors, M. Taillefer rg. Lett. 2011, 13, a) A. Tlili,. Xia, F. Monnier, M. Taillefer Angew. Chem., Int. Ed., 2009, 48,

32 IL9 ITERACTIS I IIC LIQUIDS PRBED BY MR SPECTRSCPY: DISTACES, CFRMATIS, AD MRE R. Giernoth, A. Broehl, Y. Lingscheid University of Cologne, Department of Chemistry, Koeln, Germany ne often-mentioned aspect of ionic liquids (ILs) is that they are designer solvents whose properties can be designed for any particular need [1]. bviously, it is impossible to choose a different property for a given IL but only a different IL entirely. To be able to sensibly do so, it is necessary to know about the supramolecular structures and the governing interactions in the ionic liquid phase. MR spectroscopy and the nuclear overhauser effect spectroscopy (E) in particular is the method of choice for the investigation of ion pair interactions [2]. The E arises due to inter- and intramolecular cross relaxation. To be able to precisely measure interactions in solution, an internal distance standard is needed. We have synthesized a monofluorinated ionic liquid which was subsequently employed in E-based MR investigations for the determination of distances and interactions in the ionic liquid phase. In a different project, we are studying the influence of different ionic liquids on peptide conformations, much in accord with the well-known Hofmeister series of ions [3]. With the help of a model system we are going to demonstrate that the choice of ions has a strong effect on the tertiary structure of different peptides in solution, and how these effects can be used for new non-native peptide chemistry. References [1] for reviews see: J.P. Hallett, T. Welton, Chem. Rev., 2011, 111, ; E. J. Maginn, J. Phys. Condens. Matter, 2009, 21, [2] P. S. Pregosin, Pure Appl. Chem., 2009, 81(4), ; Y. Lingscheid, S. Arenz, R. Giernoth, ChemPhysChem 2012, 13, [3] F. Hofmeister, Arch. Exp. Pathol. Pharmakol., 1888, 64,

33 IL10 APPLICATI F α-cf 3 -SUBSTITUTED DIAZCMPUDS I RGAIC SYTHESIS AD CATALYSIS S.. sipov, D.V. Vorobyeva, I.E. Tsishchuk A.. esmeyanov Institute of rganoelement Compounds, Russian Academy of Sciences, Moscow An efficient pathway to multifunctional CF 3 -containing aromatic, heteroaromatic and heterocyclic compounds, including cyclic amino carboxylic and amino phosphonic acid derivatives have been developed. The method is based on in situ generation of highly electrophilic CF 3 -carbene species from the corresponding α-diazo carboxylates or phosphonates under Cu- or Rh-catalysis and their reactions with appropriate nucleophilic partners. 1-4 The further applications of the reaction products in metal-catalysed transformations of different types, e.g. such as ring closing diene and ene-yne metathesis, intramolecular Pauson-Khand reaction as well as [2+2]-cycloaddition, open an access to new families of fluorinated molecules. References: 1. D.V. Vorobyeva, A.K. Mailyan, A.S. Peregudov,.M. Karimova, T.P. Vasilyeva, I.S. Bushmarinov, C. Bruneau, P.H. Dixneuf, S.. sipov, Tetrahedron, 2011, 67, A.K. Mailyan, I.M. Krylov, C. Bruneau, P.H. Dixneuf, S.. sipov, Synlett, 2011, A.K. Mailyan, I.M. Krylov, C. Bruneau, P.H. Dixneuf, S.. sipov, Eur. J. rg. Chem., 2013, I.E. Tsishchuk, D.V. Vorobyeva, A.S. Peregudov, S.. sipov, Eur. J. rg. Chem. 2014,

34 IL11 EW ADVACES I RGAMETALLIC AD PHSPHRUS ELECTRCHEMISTRY D.G. Yakhvarov,.G. Sinyashin A.E.Arbuzov Institute of rganic and Physical Chemistry, Laboratory of rganometallic and Coordination Compounds, Kazan, Russian Federation The development of modern chemical science and creation of new industrially applicable technologies are focused on application of effective and ecologically safe methods for the preparation of important and useful chemical compounds and materials. The combination of transition-metal catalysis and organic electrosynthesis has attracted increasing attention due to the high selectivity and efficiency of this approach in the synthetic preparation of various compounds bearing carbon-carbon and carbon-element bonds. The mild conditions, single-stage process, cyclic regeneration of the catalyst, and convenient and relatively inexpensive form of the energy used are the main advantages of electrochemical methods. Application of electrochemical processes to largescale production (macroscale synthesis) has led to significant development of the chemical technologies of the 21st century, due to easy access to highly reactive intermediates and tuning of the reactivity of the substrate used during the synthetic process by simple adjustment of the electrode potential. The elaborated in our research group electrochemical methods have been successfully applied for generation of organometallic sigma-complexes, 1 which are important intermediates of different carbon-carbon and carbon-element coupling processes, selective preparation of organophosphorus compounds from white phosphorus, 2 activation of inert oligophosphorus moieties formed in the coordination sphere of transition metal complexes, 3 selective cleavage of the tungsten-phosphorus bond resulting in valuable metal-free phosphorus heterocycles obtained via phosphinidene intermediates. 4 Herein, we present recent advances in synthetic application of the electrochemical techniques for preparation and activation of organonickel complexes 1 and generation of new, previously known as unstable, phosphorus intermediates, 5 which can be applied for preparation of practically useful organophosphorus compounds, transition metal catalysts and magnetically active materials. 6 Acknowledgements: Financial support from the Russian Scientific Fund (project ) and Russian Foundation for Basic Research (project a) is gratefully acknowledged. References: [1] D.G.Yakhvarov, A.F.Khusnuriyalova,.G.Sinyashin. rganometallics, 2014, in press. [2] D.G.Yakhvarov, E.V.Gorbachuk,.G.Sinyashin. Eur. J.Inorg.Chem., 2013, [3] D.Yakhvarov, P.Barbaro, L.Gonsalvi, S.Mañas, S.Midollini, A.rlandini, M.Peruzzini,.Sinyashin, F.Zanobini. Angew. Chem. Int. Ed., 2006, 45, [4] D.G.Yakhvarov, Yu.H.Budnikova,.H.Tran Huy, L.Ricard, F.Mathey. rganometallics, 2004, 23, [5] D.Yakhvarov, M.Caporali, L.Gonsalvi, Sh.Latypov, V.Mirabello, I.Rizvanov,.Sinyashin, P.Stoppioni, M.Peruzzini. Angew. Chem.Int.Ed., 2011, 50, [6] D.Yakhvarov, E.Trofimova,.Sinyashin,.Kataeva, P.Lönnecke, E.Hey-Hawkins, A.Petr, Yu.Krupskaya, V.Kataev, R.Klingeler, B.Büchner. Inorg. Chem., 2011, 50,

35 IL12 TRIFLURMETHYLATI BY SULIGHT-PRMTED PHTREDX CATALYSIS T. Koike, M. Akita Tokyo Institute of Technology, Chemical Resources Laboratory, Yokohama, Japan Photoredox catalysis 1 mediated by photo-sensitizers (e.g. [Ru(bipy) 3 ] 2+ and relevant Ir complexes) has attracted increasing attention as practical, green synthetic chemical processes, because they are visible light-promoted, redox-neutral reactions. We have demonstrated that photoredox catalysis is a powerful synthetic tool, in particular, for trifluoromethylation of olefinic substrates, which is the topic of the presentation. 2,3 In all cases, electron transfer from the photoexcited metal species to an electrophilic CF 3 -reagent generates the key CF 3 radical intermediate together with the cationic species of the catalyst. Subsequent addition of the CF 3 radical to the olefinic substrate followed by oxidation of the resultant carbon radical intermediate by the cationic metal species gives the carbocationic intermediate, which is trapped by nucleophiles or deprotonated to furnish the coupling products. The sequential redox processes make the system redox-neutral. It is remarkable that the reactions are promoted not only by artificial light sources (e.g. Xe lamp and blue LED lamps) but also by sunlight. References: 1) C. K. Prier, D. A. Rankic, and D. W. C. MacMillan, Chem. Rev., 113, 5322 (2013). 2) T. Koike and M. Akita, (a) Synlett., 24, 2492 (2013); (b) Topics in Cat., 259, in press (2014) (DI: /s ). 3) Y. Yasu, T. Koike, M. Akita et al., (a) Angew. Chem., Int. Ed., 51, 9567 (2012); (b) Chem. Commun., 49, 2037 (2013); (c) rg. Lett., 15, 2136 (2013); (d) rg. Lett., 16, in press (2014) (DI: /ol403500y); (e) Beilstein J. rg. Chem., submitted; (f) to be submitted; see also (g) Chem. Commun., 48, 5355 (2012); (h) ibid., 49, 7249 (2013). 35

36 IL13 CYCLIC HYPERVALET IDIE REAGETS: A TREASURE F REACTIVITY FR CATALYSIS AD SYTHESIS J. Waser Ecole Polytechnique Federale de Lausanne, ISIC SB LCS, Lausanne, Switzerland The non-classical four electrons three centers bonds of hypervalent iodine are weaker than normal classical bonds. This confers an exceptional reactivity to these compounds as oxidants or atomtransfer reagents. Cyclic hypervalent iodine reagents are especially interesting, as they combine enhanced stability with unique opportunities for reactivity modulation. In particular, our group has been interested in the development of alkynylation methods using cyclic EthynylBenziodoXolone (EBX) hypervalent iodine reagents. 1 Interesting recent results of our research in the area includes the first example of gold-catalyzed domino cyclization-alkynylation 2 and a highly efficient and practical alkynylation method for thiols. 3 Herein, we will present our most recent work in the area of electrophilic alkynylation, as well as the extension of the use of cyclic hypervalent iodine reagents to other functionalization reactions. References: 1. J.P Brand, J. Waser, Chem. Soc. Rev. 2012, 41, Y. Li, J. P. Brand, J. Waser, Angew. Chem., Int. Ed. 2013, 52, R. Frei, J. Waser, J. Am. Chem. Soc. 2013, 135,

37 IL14 THERY AD CMPUTATI PRVIDE ISIGHTS AD DISCVERY CHEMICAL REACTIS F CMPLEX MLECULAR SYSTEMS K. Morokuma 1,2 1 - Fukui Institute for Fundamental Chemistry; Kyoto University, Kyoto, Japan 2 - Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA, USA The chemical reaction that creates, destroys, reorganizes chemical bonds to produce new compounds is the most important subject of chemistry. Theoretical/computational studies have come a long way and are now playing the central role in providing insights in understanding the mechanism and dynamics of chemical reactions as well as in discovery of new reaction mechanisms and reaction systems. The theory can study not only the reaction of the ground state of molecules in gas phase but also reactions of excited electronic states as well complicated reactions of complex molecular systems. The information theoretical/computational studies can provide is often complementary to the information experimental studies provide, and research on chemical reactions is becoming impossible without strong collaboration between theorists and experimentalists. In the present talk, I will discuss some of our recent studies of chemical reactions. We have developed the Global Reaction Route Mapping (GRRM) strategy for automatic exploration of reaction pathways of complex molecular systems. The ADDF (anharmonic downward distortion following) and the AFIR (artificial force induced reaction) methods in the GRRM strategy have been used for determination of not only energy minima and saddle points on the potential energy hypersurfaces but also minima and saddle points on the conical intersection and crossing seam hypersurfaces. I will discuss the GRRM strategy and applications to several reaction systems, including photodissociation reactions, catalytic reactions and enzymatic reactions. 37

38 IL15 CMPUTATIAL ISIGHTS IT C-H FUCTIALIZATI JUGLE D. Musaev Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia, U.S.A I will present our integrated and collaborative approaches to the Transition metal catalyzed C-H bond functionalization. I will elaborate our efforts on understanding the transition metal catalyzed C-H bond alkylation and amination reactions, and analyze the factors controlling the reactivity of these reactions and make intriguing predictions. I will discuss our latest SELECTIVE RSH/RSeH + C C ZR ZR ZR Pd Pd Pd RZ ZR ZR ZR Active ZR Pd Pd Inactive ZR ZR RZ Pd ZR Pd-cluster effect C-H FUCTIALIZATI Pd(II)- PRECATALYST DIRECT Ar-Ar CUPLIG Ph Ar PR 3 "Cs 2 -I-F" assisted results [1] on the mono-protected amino acid ligands (MPAA) promoted Pd(II)-catalyzed enantioselective C H activation reactions. The presented computation allowed us to gain insights into the mechanisms, nature of active species, a ligand coordination mode to the Pd(II) and transition state structure of the C H activation step. ur findings were supported by experiments. [1] D. G. Musaev, T. M. Figg, and A. L. Kaledin, Chem. Soc. Rev., DI: /C3CS60447K, (2014). Cs I Pd F H Cs Base (Cs)-effect i-pr H Pd H PG H Ph Ligand accelerated Protecting Group effect - 38

39 IL16 A VEL TRIFLURMETHAESULFYL HYPERVALET IDIUM YLIDE FR TRIFLURMETHYLTHILATI. Shibata agoya Institute of Technology, Department of anopharmaceutical Sciences, agoya, Japan In the last few decades, numerous methods for the introduction of a trifluoromethylthio group into organic compounds have been developed. The main strategies are indirect methods, including halogen-fluorine exchange and trifluoromethylation of sulfur-containing compounds, such as disulfides, thiols and thiolates. bviously, the most attractive and ideal route to constitute the CF3S moiety is the direct introduction of this functional group. However, in this approach, some limitations are usually encountered, including the use of gaseous and highly toxic reagents, such as CF3SCl, or unstable reagents, and the modest scope of substrates. Although several transition metal-mediated or catalyzed trifluoromethylthiolation methods have been developed, the substrates are mostly limited to aromatic compounds. Recently, Billard and co-workers reported that trifluoromethanesulfanylamides were effective for trifluoromethylthiolation of alkenes, alkynes, indoles and organometallic species. More recently, Lu and Shen also developed a novel hypervalent iodine reagent for the trifuoromethylthiolation of aryl and vinyl boronic derivatives, alkynes and β- ketoesters. Even though these direct trifluoromethylthiolation reagents are shelf-stable, a more critical issue is the fact that these CF 3 S regents should be prepared in advance by trifluoromethylthiolations or related trifluoromethylations! Due to these limitations and negative aspects, it is thus still necessary to develop an efficient and easily available reagent to introduce the CF 3 S moiety directly. In contrast to the CF 3 S unit, a trifluoromethanesulfonyl (CF 3 S 2 ) unit is stable and often found in commonly used organic reagents such as CF 3 S 2 Cl, CF 3 S 2 a, CF 3 S 2 H and (CF 3 S 2 ) 2. In this context, we came up with a novel idea of using ubiquitous CF 3 S 2 compounds as reagents for introducing the CF 3 S unit under reductive conditions. As a part of our recent work on the chemistry of trifluoromethanesulfonyl compounds (triflones), we herein disclose a novel trifluoromethanesulfonyl hypervalent iodonium ylide as a shelf-stable reagent for electrophilic-type trifluoromethylthiolation. A wide variety of nucleophiles are nicely converted into the corresponding trifluoromethylsulfanyl products by this reagent. Reference: Y.-D. Yang, A. Azuma, E. Tokunaga, M. Yamasaki, M. Shiro,. Shibata, J. Am. Chem. Soc., 135, 8782 (2013) 39

40 IL17 CATALYSIS-ASSISTED SIGAL EHACEMET I UCLEAR MAGETIC RESACE I.V. Koptyug International Tomography Center, SB RAS, ovosibirsk, Russia When parahydrogen (nuclear spin isomer of H 2 ) is used in catalytic hydrogenations instead of normal H 2, the MR signals of reaction products and intermediates can be enhanced by 3-4 orders of magnitude and more owing to the phenomenon of parahydrogen-induced polarization (PHIP). This possibility has been explored previously in the context of activation of H 2 by transition metal complexes and clusters in solution. It has been shown that PHIP can help to detect reaction products and short-lived intermediates not detectable by conventional MR. As most of the industrial catalytic processes are heterogeneous, it would be desirable to employ PHIP in the MR studies of heterogeneous catalysts and catalytic reactions. The objective of our research is thus to extend the scope of PHIP applications to the heterogeneously (HET) catalyzed hydrogenation reactions, and to develop a hypersensitive MR-based technique for the in situ and operando studies of heterogeneous catalytic processes. In addition, HET-PHIP can be employed to produce catalyst-free hyperpolarized liquids and gases for novel MRI applications including the advanced in vivo studies. We demonstrate that, similar to their homogeneous counterparts, heterogenized transition metal complexes are able to produce strong MR signal enhancements when parahydrogen is used in the hydrogenation reactions [1]. ur recent results show that various immobilized metal complexes are can produce HET-PHIP both in liquid phase and in gas phase hydrogenations. In contrast, for supported metal catalysts (e.g., Pt/Al 2 3 ), dissociative hydrogen chemisorption and rapid migration of H atoms on the metal surface were expected to make the required pairwise hydrogen addition to a substrate molecule impossible. evertheless, we have shown that PHIP can be successfully observed both in liquid-solid and in gas-solid heterogeneous hydrogenations catalyzed by supported metal catalysts [1]. The MR signal enhancement was found to be sensitive to the metal nanoparticle size and shape, the nature of the metal and support, and the type of substrate used in the reaction. Recently, HET-PHIP effects were also demonstrated for several metal oxides and bulk unsupported metals used as hydrogenation catalysts [2]. The implications of these results for the mechanisms of heterogeneous hydrogenation processes are discussed [1,3]. Further potential extensions of the technique will be presented, including the use of metal-free catalysts for activating parahydrogen [4], and the prospects of using nuclear spin isomers of molecules other than H 2 to further extend the range of reactions and processes that can be explored in detail using the PHIP technique [5]. In addition to applying HET-PHIP to the mechanistic and kinetic studies of heterogeneous hydrogenations, several MRI applications of HET-PHIP have been already demonstrated, including MR imaging of a catalytic reaction in an operating model microreactor [6]. 1. K.V. Kovtunov, V.V. Zhivonitko, I.V. Skovpin, D.A. Barskiy, I.V. Koptyug, Top. Curr. Chem., 338, 123 (2013). 2. K.V. Kovtunov, D.A. Barskiy,.G. Salnikov, A.K. Khudorozhkov, V.I. Bukhtiyarov, I.P. Prosvirin, I.V. Koptyug, Chem. Commun., 50, 875 (2014) 3..G. Salnikov, K.V. Kovtunov, D.A. Barskiy, A.K. Khudorozhkov, E.A. Inozemtseva, I.P. Prosvirin, V.I. Bukhtiyarov, I.V. Koptyug, ACS Catal., 4, 2022 (2014). 4. V.V. Zhivonitko, V.-V. Telkki, K. Chernichenko, T.J. Repo, M. Leskela, V. Sumerin, I.V. Koptyug, J. Amer. Chem. Soc., 136, 598 (2014). 5. V.V. Zhivonitko, K.V. Kovtunov, P.L. Chapovsky, I.V. Koptyug, Angew. Chem. Int. Ed., 52, (2013). 6. V.V. Zhivonitko, V.-V. Telkki, I.V. Koptyug, Angew. Chem. Int. Ed., 51, 8054 (2012). 40

41 IL18 -BD ACTIVATI REACTI BY TRASITI METAL AD MAI- GRUP ELEMET CMPUDS AD CATALYTIC REACTI ICLUDIG IT S. Sakaki Fukui Institute for Fundamental Chemistry, Kyoto University, Takano, Sakyo-ku, Kyoto , Japan The -bond activation by transition metal complexes attracts a lot of interests in theoretical and organometallic chemistries, because it is crucial in many catalytic reactions by transition metal complexes. In our understanding, -bond activation is classified to two categories; the concerted oxidative addition to M (metal), the stepwise oxidative addition via nucleophilic attack, the oxidative addition to M-L (L = neutral ligand), and the heterolytic activation by M-X (X = anionic ligand). activation by metal center only and that by the metal-ligand moiety. 1,2 ML n + R1-R2 cis-ml n (R 1 )(R 2 ) (1) ML n + R1-X [ML n (R 1 )] --(X) trans-mx(r 1 )L n (2) MLL n + R1-R2 ML n (R 1 )(L-R 2 ) (3) MXL n + R1-R2 ML n (R 1 ) + R 2 -X (4) We theoretically investigated these reactions and elucidated the characteristic electronic processes and clear understanding. 2 We also theoretically investigated catalytic reactions including -bond activation. In this talk, we wish to present our recent theoretical studies of carboxylation of phenylchloride catalysed by a nickel(0) complex, hydrosilylation of carbon dioxide catalyzed by germanium(ii)- and zinc(ii)-hydride compounds. 3 In my talk, I wish to present comprehensive understanding of these -bond activation reactions and the importance of -bond activation reaction in such catalytic reactions as C 2 conversion and cross-coupling reactions. References. 1. S. Sakaki, Y.-y. hnishi, H. Sato, Chem. Record., 10, 29 (2010). W. Guan, F. B. Saeed, S. Sakaki, Inorg. Chem., in press. 2.. chi, Y. akao, H. Sato, S. Sakaki, J. Am. Chem. Soc., 129, 8615 (2007).. chi, Y. akao, H. Sato, S. Sakaki, J. Phys Chem. A, 114, 659 (2010). 3.. Takagi and S. Sakaki, J. Am. Chem. Soc., 135, 8955 (2013). M. Deschmukh, to be submitted. 41

42 IL19 PLAAR HETERARMATICS: SYTHESIS AD SELF-ASSEMBLY M. Stepien Wydziaі Chemii, Uniwersytet Wrocіawski Even though π-electron aromaticity is typically associated with planar structures, several classes of distorted π-aromatics are known, including a variety of twisted, helical, bowl-shaped, or tubular systems. Such distortions are of fundamental interest, because they provide a means of testing different aspects of aromaticity theory, but they also may have practical consequences, as a potential method of fine-tuning the electronic structure and self-assembly properties of aromatic compounds. In this contribution, two synthetic approaches to nonplanar heteroaromatics will be discussed. ne is based on oxidative coupling reactions of pyrrole-containing precursors, and is exemplified by our recent syntheses of peripherally fused porphyrin derivatives 1 (1 and 2) and bipyrroles. 2 Compounds 1 2 are characterized by bathochromically shifted electronic absorptions and very high extinction coefficients. Phenanthroporphyrins 1 and their complexes reveal substitution-dependent aggregation in solution and form columnar mesophases in the condensed phase. The zinc(ii) complex of benzochrysenoporphyrin 2 was found to form a unique 3D-ordered mesophase containing discrete multiporphyrin aggregates. The other approach to nonplanar aromatics explored in our laboratory, which is suitable to the synthesis of bowl- or belt-shaped structures, involves the so-called fold-in synthesis, 3 performed on appropriately designed macrocyclic precursors. The fold-in concept can be realized using different reactivity types, including Ullmann-type reductive coupling, as in the recent synthesis of chrysaorole (3), 3,4 and Friedel Crafts alkylation. 5 (1) Myśliwiec, D.; Donnio, B.; Chmielewski, P. J.; Heinrich, B.; Stępień, M. J. Am. Chem. Soc. 2012, 134, (2) Gońka, E.; Myśliwiec, D.; Lis, T.; Chmielewski, P. J.; Stępień, M. J. rg. Chem. 2013, 78, (3) Stępień, M. Synlett 2013, 24, (4) Myśliwiec, D.; Stępień, M. Angew. Chem. Int. Ed. 2013, 52, (5) Kondratowicz, M.; Myśliwiec, D.; Lis, T.; Stępień, M. in preparation. 42

43 IL20 RHDIUM -HETERCYCLIC CARBEE CMPLEXES AS EFFICIET CATALYSTS FR X-H ADDITIS T ALKYES: THE QUEST FR SELECTIVITY R. Castarlenas, A. Di Giuseppe, L. Rubio-Perez, L. Palacios, R. Azpiroz, V. Polo, J.J. Perez- Torrente, L.A. ro ISQCH Universidad de Zaraaragoza-CSIC The development of new catalytic systems for the synthesis of added-value products in a selective manner and with high atom economy is nowadays an important task. In this context, our group has recently prepared new rhodium complexes bearing an -heterocyclic carbene (HC) ligand that have been disclosed to be very active and gem-selective for X-H additions across C-C triple bonds. 1-4 Experimental and theoretical (DFT) mechanistic studies indicate that the presence of a bulky powerful electron-releasing HC and the rational choice of the auxiliary ligands is essential in order to control the selectivity towards the formation of Markonikov-type products. 1 A. Di Giuseppe, R. Castarlenas, J.J. Perez-Torrente, M. Crucianelli, V. Polo, R. Sancho, F.J. Lahoz, L.A. ro, J. Am. Chem. Soc. 2012, 134, L. Palacios, M.J. Artigas, V. Polo, F.J. Lahoz, R. Castarlenas, J.J. Perez-Torrente, L.A. ro, ACS Catal. 2013, 3, L. Rubio-Pérez, R. Azpíroz, A. Di Giuseppe, V. Polo, R. Castarlenas, J.J. Perez-Torrente, L.A. ro, Chem. Eur. J. 2013, 19, R. Azpíroz, A. Di Giuseppe, R. Castarlenas, J.J. Perez-Torrente, L.A. ro, Chem. Eur. J. 2013, 19,

44 IL21 CATALYTIC LEFIATI REACTI UIVERSAL METHD FR SYTHESIS F ALKEES V.G. enajdenko Moscow State University, Department of Chemistry, Leninskie Gory, Moscow Catalytic olefination reaction represents new approach to the preparation of double C=C bond. - unsubstituted hydrazones can be converted into alkenes by treatment with polyhalogenated alkanes in presence of a base and catalytic amounts of copper salts. The reaction has a wide synthetic scope allowing to prepare both alkyl and aryl halogenoalkenes, including fluorinated ones and derivatives with functional groups. Simple experimental procedure, which does not require using of organometallic or toxic organophospourous compounds, affordable price and availability of starting materials, high yields and stereoselectivity are distinct advantages of the reaction. R 1 C R 1 R 2 F F R 1 R 2 Br Br R 1 R 2 Cl Cl R 1 R 2 Cl CH 2 H R 1 H R 2 Cl R 2 Cl R 1 Cl R 1 H R 2 R 1 CR Cl R 1 R 2 R 2 R 1 Br H R 2 CR 2 R 2 I R CBrF 2 R 1 Cl R 1 R 2 F F CBrF 2 R 1 F R 1 Cl R 1 F R 1 F R 2 R 2 CBrF 2 R 2 CF 3 R 2 CClF 2 R 2 Cl 44

45 IL22 HW T MAKE CMPLEX MLECULES FRM SIMPLE STARTIG MATERIAL: THE PALLADIUM, A PWERFUL TL J. Suffert University of Strasbourg/CRS In addition to molecular complexity, the challenge of the chemist today is also the quest for efficiency of the synthetic route and maximization of structural complexity. ur laboratory investigations focus for several years on the study of an unprecedented cascade reaction involving a rare 4-exo-dig cyclocarbopalladation followed by a terminated cross-coupling with an organometallic reagent. A 6 - or 8 -electrocyclization can occur leading to new tricyclic structures. The seminar will show that we can offer an easy access to complex polycyclic molecules resulting from readily available simple starting materials. Eventually, it will be possible to propose the elaboration of a large collection of unprecedented structurally novel molecules based on recent promising results. Below are represented several complex structures that has been prepared through the powerful 4-exo-dig cyclocarbopalladation. Many other extension of this method have not been so far explored and can afford a multitude of new and original scaffolds. 45

46 IL23 SYTHESIS F TI AD LEAD AALGS F CYCLPETADIEYL AI AD THEIR APPLICATI T TRASITI-METAL CMPLEXES M. Saito Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama-city, Saitama, , Japan We succeeded in the generation of tetraphenyldilithiostannole 1a, [1] and its considerable aromatic character was established by X-ray diffraction analysis and theoretical calculations. [2] The lead analog, tetraphenyldilithioplumbole 2 was also found to be aromatic, indicating that the concept of aromaticity is expanded to lead-bearing carbon cycles. [3] After the synthesis of heavier congeners of Cp anion, attention was next paid to the preparation of transition-metal complexes with such heavier Cp ligands. The first heavier metallocene was a ruthenocene bearing a germole ligand, [4] and transition-metal complexes with silole and germole ligands have already been synthesized. The straightforward method for the synthesis of such metallocenes is the reactions of metallole anions and dianions with transition-metal reagents. However, the reactions using stannole anions and dianions had never been reported until recently. We examined the reaction of tetraphenyldilithiostannole 1b [5] with [Cp*RuCl] 4, and butterfly complex 3 was obtained instead of an expected ruthenocene. [6] The reaction of 1b with Cp 2 TiCl 2 afforded three-membered ring compound 4 with unique electronic states. [7] The synthesis of the first neutral triple-decker complex 5 with group 14 metallole ligands was also achieved using silylsubstituted dilithiostannole 1c. 1 a : 1b : 1c: 2 : R 2 R 2 L i L i R 1 M R 1 E t E t M = S n ; R 1 = R 2 = P h M = S n ; R 1 = R 2 = E t M = S n ; R 1 = M e 3 S i, R 2 = P h M = P b ; R 1 = R 2 = P h E t E t S n R u R u C p * 3 S n E t C p * E t E t E t C p C p T i S n S n 4 P h C p *R u M e 3 S i P h R u C p * S im e 3 S n 5 References [1] Saito, M.; Haga, R.; Yoshioka, M. Chem. Commun. 2002, [2] Saito, M.; Haga, R.; Yoshioka, M.; Ishimura, K.; agase, S. Angew. Chem., Int. Ed. 2005, 44, [3] Saito, M.; Sakaguchi, M.; Tajima, T.; Ishimura, K.; agase, S.; Hada, M. Science 2010, 328, 339. [4] Freeman, W. P.; Tilley, T. D.; Rheingold, A. L.; strander, R. L. Angew. Chem., Int. Ed. Engl. 1993, 32, [5] Saito, M.; Kuwabara, T.; Kambayashi, C.; Yoshioka, M.; Ishimura, K.; agase, S. Chem. Lett. 2010, 39, 700. [6] Kuwabara, T.; Saito, M.; Guo, J. D.; agase, S. Inorg. Chem. 2013, 52, [7] Kuwabara, T.; Guo, J. D.; agase, S.; Saito, M. Angew. Chem., Int. Ed. 2014, 53,

47 IL24 EW METHDS FR PERXIDE SYTHESIS A.. Terentev ZICh, Moscow, Russia In the last decades, organic peroxides have received considerable attention from chemists and drug design experts, which is associated with a need in the search for drugs for the treatment of parasitic diseases, such as malaria and helminth infections. Considerable progress has been made in the design of effective peroxide antimalarial drugs. Some synthetic peroxides exhibit activity equal to or higher than that of artemisinin. Peroxides having antitumor or growth-regulatory activity were also documented. In our work we developed new methods for synthesis of various types of peroxides. It was found that some peroxides posesses pronounced antischistosomal properties and anticancer activity. This work is supported by the Grant of the Russian Foundation for Basic Research (Grant ) and by the Program for Basic Research of the Presidium of the Russian Academy of Sciences. References [1] Terent'ev, A., Borisov, D., Yaremenko, I., Chernyshev, V., ikishin, G. J.rg.Chem. 75, , [2] Terent'ev, A., Yaremenko, I., Chernyshev, V., Dembitsky, V., ikishin, G. J.rg.Chem. 77, , [3] Ingram, K., Yaremenko, I.A., Krylov, I., Hofer, L., Terent'ev, A.., Keiser, J. J.Med.Chem. 55 (20), , [4] Terent'ev, A.., Yaremenko, I, A., Vil', V. A., Dembitsky, V. M., ikishin, G. I. Synthesis , [5] Terent'ev, A.., Yaremenko, I, A., Vil', V. A., Моisееv, I. K., Kon kov, S. A., Dembitsky, V. M., Levitsky, D.., ikishin, G I. rg. Biomol. Chem. 11, , [6] I.A. Yaremenko, A.. Terent ev, V.A. Vil, R.A. ovikov, V.V. Chernyshev, V.A. Tafeenko, D.. Levitsky, F. Fleury, G.I. ikishin. Chemistry - A European Journal DI: /chem

48 IL25 SYERGISM BETWEE THERY AD EXPERIMETS I ASYMMETRIC CATALYSIS: TRASITI STATE MDELIG FR RATIALIZATIS AD CATALYST DESIG R.B. Sunoj Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai Computational quantum chemistry has been increasingly employed toward rationalizing the stereochemical outcome of a diverse range of reactions. 1 The approach typically involves the identification of kinetically significant transition states and intermediates. In our laboratory, ab initio as well as DFT methods are employed to gain insights into carbon-carbon and carbonheteroatom bond-forming reactions of immediate practical significance. 2 The key objective is in establishing the factors responsible for stereoselectivity in such reactions and to employ those insights toward in silico design of novel catalysts for potential asymmetric applications. 3 A number of examples wherein the conventional transition state models required systematic improvements toward accounting the observed product distribution and stereochemical outcome will be presented. In general, the presentation would encompass a few contemporary themes in the domain of organo- and organo-metallic catalysis. Interesting interpretations/rationalizations of experimental observations besides meaningful guidelines for rational improvements in asymmetric catalysis would remain the key focus of the presentation. The contents are designed to cater to a broad and diverse group of audience; hence, the chemical insights would receive more emphasis, rather than intricate technical details. [1] (a) Cheong, P. H. Y.; Legault, C. Y.; Um, J. M.; Celebi-lcum,.; Houk, K.. Chem. Rev. 2011, 111, (b) Sunoj, R. B. Wiley Interdisciplinary Reviews: Comput. Mol. Sci. 2011, 1, 920. [2] (a) Shinisha, C. B.; Sunoj, R. B. J. Am. Chem. Soc. 2010, 132, (b) Sharma, A. K.; Sunoj, R. B. Angew. Chem. Int. Ed. 2010, 49, (c) Sharma, A. K.; Sunoj, R. B. Chem. Commun. 2011, 47, (d) Jindal, G.; Sunoj, R. B., Chem. Eur. J. 2012, 18, (e) Jindal, G.; Sunoj, R. B., Angew. Chem., Int. Ed. 2014, 53, (f) Anand, M.; Sunoj, R. B.; Schaefer, H. F. J. Am. Chem. Soc. 2014, 136, [3] (a) Shinisha, C. B.; Sunoj, R. B. rg. Biomol. Chem. 2007, 5, (b) Shinisha, C. B.; Sunoj, R. B. rg. Lett. 2009, 11, (c) Jindal, G.; Sunoj, R. B. rg. Bimol. Chem. 2014, 12,

49 IL26 CATALYTIC ASYMMETRIC CRTYLATI: METHD DEVELPMET AD APPLICATI I TTAL SYTHESIS A.V. Malkov, P.S. hora, C.A. Incerti-Pradillos, M.A. Kabeshov Loughborough University, Loughborough, LE11 3TU, UK Secondary metabolites 1-5 isolated from marine soft coral Pseudopterogorgia elisabethae exhibit a wide range of useful biological properties, which include anti-tubercular, anti-inflammatory, antimicrobial and analgesic activities [1]. The analgesic properties are superior to the existing industry standards. As a result, partially purified gorgonian extracts are used in commercial skin care products for topical applications [2]. H H H H H H H H H H H H (+)-Erogorgiaene (+)-Elisabethadione ( )-Elisapterosin B ( )-Colombiasin A 5 Pseudopterosin A-D aglycone Herein, we present a novel general strategy for a scalable enantioselective total synthesis of serrulatane diterpenes 1 and 2. Synthetically, a major challenge associated with the synthesis of these compounds is the control of the three stereocentres in the absence of directing functional groups. ur principal strategy is based on the asymmetric crotylation of cinnamyl-type aldehyde 10 with Z-crotyltrichlorosilane 9 to produce homoallylic alcohol 8 with a set of stereogenic centers that will be used to control the stereochemistry of oxy-cope rearrangement (8 7) and the subsequent transformations towards the advanced intermediate 6. Development of novel efficient Lewis base catalysts for the asymmetric crotylation and completion of the total synthesis of ( )-elisabethadione and ( )-erogorgiaene will be discussed in detail. R n 1,2 cationic cyclisation R n H 9 Wittig olefination H SiCl 3 R n R n H 7 H Anionic oxy-cope 10 Cat* 8 References [1] A. D. Rodriguez, C. Ramirez, J. at. Prod. 2001, 64, [2] A. Kijjoa, P. Sawanwong, Mar. Drugs 2004, 2,

50 IL27 SYTHESES F METAL CMPLEXES WITH TRAS-CYCLALKAE- 1,2-DIYL-[SS]-TYPE BIS(PHELATE) LIGAD AD ISSPECIFIC PLYMERIZATI F ALPHA-LEFIS A. Ishii Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama , Japan Efficiency and stereoselectivity of reactions catalyzed by metal complexes are often greatly affected by auxiliary ligands of the catalysts. We have recently developed tetradentate auxiliary ligands 1 featuring oxygen and sulfur coordination sites and fusion of trans-cycloalkane-1,2-diyl rings. 1 3 The [SS]-bis(phenolate) ligand 1 (n = 3) was applied to the synthesis of zirconium complex 2 and we found that a combination of 2 and an activator catalyzes the polymerization of 1-hexene with high activity and high isospecificity 1 in comparison with previously reported group 4 metal complexes bearing [SS]-type ligands. 4 We have also synthesized Ti, 5 Zr, 6 Hf, 7 V, 8 b, 8 Ta, 8 and Al 9 complexes with 1 (n = 3) and investigated catalytic reactions with these complexes. In this paper, we report the syntheses and structures of these metal complexes and their catalytic ability with recent progress. t Bu t Bu t Bu n t Bu S H S Zr S H S t Bu t Bu t Bu 1 2 CH 2 Ph CH 2 Ph t Bu Bu 2/(Ph 3 C)[B(C 6 F 5 ) 4 ] Bu Bu Bu Bu Bu activity = 2,500 g mmol 1 h 1 isotactic poly(1-hexene) ([mmmm] >95%) M w = 59,000, PDI = 1.7 References 1. Ishii, A.; Toda, T.; akata,.; Matsuo, T. J. Am. Chem. Soc. 2009, 131, Ishii, A.; Toda, T.; akata,.; Matsuo, T. Phosphorus, Sulfur, Silicon 2011, 186, Ishii, A.; Asajima, K.; Toda, T, akata,. rganometallics 2011, 30, akata,.; Toda, T.; Ishii, A. Polym. Chem. 2011, 2, akata,.; Toda, T.; Matsuo, T.; Ishii, A. Inorg. Chem. 2012, 51, Toda, T.; akata,.; Matsuo, T.; Ishii, A. J. rganomet. Chem. 2011, 696, akata,.; Toda, T.; Matsuo, T.; Ishii, A. Macromolecules 2013, 46, ; akata,.; Saito, Y.; Watanabe, T.; Ishii, A. Top. Catal. 2014, 57, Toda, T.; akata,.; Matsuo, M.; Ishii, A. ACS Catal. 2013, 3, akata,.; Saito, Y.; Ishii, A. rganometallics 2014, 33,

51 IL28 EW APPRACH FR THE SYTHESIS F CMPUDS CTAIIG CF 2 FRAGMET A.D. Dilman, V.V. Levin, A.A. Zemtsov, M.D. Kosobokov. D. Zelinsky Institute of rganic Chemistry Existing methods for the synthesis of compounds containing CF 2 fragment either employ hazardous reagents or require long synthetic sequence. We propose a new approach towards difluorinated compounds based on the coupling of three components nucleophile, difluorocarbene and electrophile. As nucleophiles, organometallic reagents can be employed. The insertion of difluorocarbene into carbon-zinc bond of organozinc reagents leads to new organozinc species, which can be quenched by halogen or proton, 1 or coupled with allylic electrophiles. 2 The interaction of trimethylsilyl cyanide with difluorocarbene affords difluoro(trimethylsilyl)- acetonitrile. This reagent was used in reactions with aldehydes and imines furnishing fluorinated alcohols and amines. 3 The addition products can be transformed into a variety of heterocyclic molecules. 4 This work was supported by the Ministry of Science (project MD ) and Russian Foundation for Basic Research (projects , , _mol_a, _mol_a). 1. Levin, V. V.; Zemtsov, A. A.; Struchkova, M. I.; Dilman, A. D. rg. Lett. 2013, 15, Zemtsov, A. A.; Kondratyev,. S.; Levin, V. V.; Struchkova, M. I.; Dilman, A. D. J. rg. Chem. 2014, 79, Kosobokov, M. D.; Dilman, A. D.; Levin, V. V.; Struchkova, M. I. J. rg. Chem. 2012, 77, Kosobokov, M. D.; Struchkova, M. I.; Arkhipov, D. E.; Korlyukov, A. A.; Dilman, A. D. J. Fluorine Chem. 2013, 154,

52 IL29 TWARDS REALISTIC FIRST-PRICIPLES MDELLIG F CMPLEXITY I HETERGEEUS CATALYSIS K.M. eyman ICREA and Universitat de Barcelona Active components present in heterogeneous catalysts as nano-aggregates of thousands atoms remain inaccessible for the first-principles (based on DFT) computations due to their size and complexity. However, such species could be rather realistically represented by computationally tractable smaller model nanoparticles (Ps), whose surface sites only marginally change the reactivity with increasing particle size. We illustrate this for decomposition of methane 1 and methanol 2-4 on Pt and Pd catalysts as well as building of active sites on Pt/ceria catalysts. 5,6 We show that using common slab models and thus neglecting the nanoscopic effects in these and similar systems could lead to severe misrepresentation of the surface reactivity. 7 Methane decomposition on Pt P is calculated to be more exothermic than on Pt(111) surface and proceed via much lower activation barriers for the rate-limiting steps. 1 The reason for Pt activation by nanostructuring is that CH x species are stabilized on P edges, converting the first two steps of CH 4 decomposition from endothermic on Pt(111) to exothermic on Pt 79. The higher activity of edge Pt atoms was assigned to their lower coordination and higher flexibility. The flexibility affects not only adsorption properties of sites with low-coordinated atoms but also nearby terrace sites. This effect is most pronounced for strongly bound adsorbates, e.g atomic C. It is a common by-product in decomposition reactions on Pd, 2 able to modify catalyst properties upon exothermic migration subsurface. 3,4 The most spectacular effect of flexibility of Pd Ps is on the subsurface migration barriers of surface C. ear Ps edges these barriers essentially vanish. Presence of subsurface C makes Pd Ps more transparent for subsurface diffusion of adsorbed hydrogen, 3 which in turn enables sustainable hydrogenation of olefins on Pd catalysts. Strong metal-support interactions can radically modify surface chemistry. Due to catalysts complexity the microscopic origin of such effects is usually unresolved. However, our study on models of Pt-ceria catalysts succeeded to uncover atomic details of interactions in this system. 5 Calculations identified two types of oxidative Pt-ceria interactions: electron transfer from a Pt particle to the support and transport from ceria to Pt. The former is favorable on ceria supports regardless their morphology. But the transfer requires the presence of Pt in close contact with nanostructured ceria, being inherently a nano-effect. Both effects were detected by monitoring the Ce 3+ /Ce 4+ ratio using resonant photoelectron spectroscopy on Pt-Ce 2 model catalysts. These case studies reveal very significant differences in the surface reactivity derived from customary slab-model calculations and those employing dedicated P models. The latter expose a variety of active sites, whose structure and geometric flexibility notably better match those of the sites present under experimental conditions. Thus, we advocate much broader usage of suitable P models in catalysis from first principles. 1. F. Viñes, Y. Lykhach, T. Staudt, M. P. A. Lorenz, C. Papp, H.-P. Steinrück, J. Libuda, K. M. eyman, A. Görling - Chem. Eur. J. 2010, 16, I. V. Yudanov, A. V. Matveev, K. M. eyman,. Rösch - J. Am. Chem. Soc. 2008, 130, K. M. eyman, S. Schauermann - Angew. Chemie Int. Ed. 2010, 49, H. A. Aleksandrov, F. Viñes, W. Ludwig, S. Schauermann, K. M. eyman - Chem. - Eur. J. 2013, 19, G.. Vayssilov, Y. Lykhach, A. Migani, T. Staudt, G. P. Petrova,. Tsud, T. Skála, A. Bruix, F. Illas, K. C. Prince, V. Matolín, K. M. eyman, J. Libuda - ature Mater. 2011, 10, A. Bruix, Y. Lykhach, I. Matolínová, A. eitzel, K. C. Prince, V. Potin, F. Illas, V. Matolín, J. Libuda, K. M. eyman, et al. - Angew. Chemie Int. Ed. 2014, 53, doi: /anie S. M. Kozlov, K. M. eyman - Top. Catal. 2013, 56,

53 IL30 С-С TRIPLE BD ACTIVATI BY PLATIUM METALS UDER HM- AD HETERGEEUS CDITIS: DESIG F EW CATALYTIC REACTIS S.A. Mitchenko L.M. Litvinenko Institute of Physical rganic and Coal Chemistry, ational Academy of Sciences of Ukraine, Donetsk, Ukraine Petroleum and natural gas are the main sources of raw materials for modern bulk and fine chemical industry. Since the middle of the last century this changed the industry redirecting technology previously based on acetylene towards olefinic stuff and synthesis gas. evertheless, series of largescale (for example, manufacture of vinyl ethers, pyrrolidone and -methylpyrrolidone, butanediol, etc.) and fine (drugs and fragrances, crop protecting agents, etc.) chemical production based on acetylene hydrocarbons possesses definite advantages and is still developing. Besides, acetylene hydrocarbons are inevitably formed as by-products in oil processing yielding olefins, and taking into account the modern industrial scales and prices of starting materials these by-products should be efficiently utilized. n the other hand, coal and natural gas supply as against of petroleum allow us to regard them as practically inexhaustible source of acetylene. Increasing interest to the catalytic chemistry of acetylene (see, for example, [1, 2]) can be motivated in particular by these considerations. Results of development of new catalytic transformations of acetylene under homo- and heterogeneous conditions will be presented and discussed. References: 1. Alonso F., Beletskaya I.P., Yus M. Chem. Rev., 2004, 104, Ananikov V. P., Beletskaya I. P. rganometallics, 2012, 31,

54 IL31 SYERGISTIC EFFECTS I DESIGIG CMBIED CATALYTIC SYSTEMS (CMBICAT S) FR ABATEMET F ITRGE XIDES (X) A.Yu. Stakheev Zelinsky Institiute of rganic Chemistry, Catalysis division, Moscow, Russia Anthropogenic emission on nitrogen oxides ( x =, 2, 2 ) becomes an important issue, since the amount of anthropogenic x nowadays exceeds biogenic emission (~110 Mt vs. 80 Mt/annual) and their impact on environment is significant. The most effective method for abatement of nitrogen oxides is their selective catalytic reduction (SCR) by urea or H 3 : 2 + 2H 3 + 1/2 2 = H 2 However, activity of the traditional H 3 -SCR catalysts at the temperatures below 250 o C is not sufficient due to the stringent restrictions imposed by environmental legislations on x emission from mobile sources. The effective solution can be provided by Cu-containing zeolite catalyst, however high cost often limits their practical application. ur recent study revealed alternative approach and indicated that promising H 3 -Dex activity at T react. < 250 C CA BE ATTAIED VER combined catalysts (CombiCat) comprising zeolite component (possessing high activity in SCR) and a redox component (having high activity in oxidation). For such compositions we found a pronounced synergistic effect and the catalytic activity of the CMBICAT S significantly exceeds activity of the individual components. A number of compositions have been tested for searching synergistic effects and the most remarkable results have been observed for [Cu/Al 2 3 +FeBETA], [Mn/Al FeBETA, [CeZr +FeBETA], [Mn/CeZr + FeBETA], Mn/FeBETA. Interestingly that the studied composition exhibits favorable performance in selective oxidation of H 3 : 2H 3 + 3/2 2 = 2 + 3H2 Therefore CombiCat s are capable to accomplish two functions: SCR catalyst and removal of residual H3. In addition to that, for the compositions comprising Ce2-Zr2 component a promising soot oxidation activity has been observed Detailed study of a possible origin of the observed synergistic effects suggests that the improvement of H3-Dex activity can be attributed to a dual function reaction mechanism comprising two main stages: (1) over redox component (2) H H 2 over zeolite component However, further research is required for revealing overall reaction network and understanding reaction mechanism responsible for observed synergy. 54

55 IL32 VEL CLCHICIIDS AS PTETIAL ATITUMR AGETS A. Yu. Fedorov Department of rganic Chemistry, izhny ovgorod State University, Gagarina av. 23, izhny ovgorod , Russian Federation A range of indole - and furane-containing allocolchicinoids was synthesized: Several from synthesized compounds manifested high in vitro and in vivo antitumor activity. Acknowledgment We thank the Russian Foundation for Basic Research (projects and a), The Ministry of Education and Science of The Russian Federation (project /K). The research is partly supported by the grant 02.В of The Ministry of Education and Science of the Russian Federation to Lobachevsky State University of izhni ovgorod. 55

56 IL33 EATISELECTIVE CATALYSIS BY CHIRAL BRØSTED ACIDS AD CHIRAL BRШSTED BASES M. Terada Tohoku Univsersity, Department of Chemistry, Sendai, Japan Chiral phosphoric acids 1 have become one of the most versatile types of chiral Brønsted acid catalysts identified to date and have been applied to a broad range of enantioselective transformations. 1,2) In my continuing efforts to broaden the scope of enantioselective catalysis by 1, activation of oxygenated functional groups other than imines and related functional groups is our recent research interest. To expand the scope of chiral Brønsted acid catalysis, recently a novel chiral bis-phosphoric acid 2 was developed as a highly active and efficient enantioselective catalyst. 3) n the other hand, intense interest has been devoted to the development of chiral uncharged organosuperbase catalysts during the past decade. In an effort to develop efficient chiral organobase catalysts, we designed and synthesized unique axially chiral Brønsted base 3. 4) 3 functioned as the efficient enantioselective catalysts for the activation of pro-nucleophile having a relatively acidic proton such as 1,3-dicarbonyl compounds. To expand the scope of chiral Brønsted Base catalysis, development of much stronger organosuperbase is highly demanded. We hence designed a pseudo C 2 -symmetric bis(guanidino)iminophosphorane 4 as a novel family of chiral organosuperbases. 5) In my presentation, I briefly introduce these chiral Brønsted acid catalysts (1 and 2) and base catalysts (3 and 4). In particular, I would like to present a novel chiral Brønsted base catalyst 4 in details. References 1) (a) Terada, M. Synthesis 2010, (b) Terada, M. Chem. Commun. 2008, ) Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004, 126, ) Momiyama,.; Konno, T.; Furiya, T.; Iwamoto, T.; Terada, M. J. Am. Chem. Soc. 2011, 133, ) Terada, M.; Ube, H.; Yaguchi, Y. J. Am. Chem. Soc. 2006, 128, ) Takeda, T.; Terada, M. Y. J. Am. Chem. Soc. 2013, 135,

57 IL34 IIC LIQUIDS, WATER AD LIQUID R SUPERCRITICAL C 2 AS PERSPECTIVE MEDIA FR ASYMMETRIC RGACATALYSIS S.G. Zlotin.D. Zelinsky Institute of rganic Chemistry Russian Academy of Sciences ver the last decade amazing results have been associated with the extensive application of asymmetric organocatalysts in organic synthesis. In the presence of small metal-free chiral organic molecules (α-amino acid or cinchona alkaloid derivatives, BIL phosphoric acids, and other chiral compounds), available prochiral reagents can be easily converted into chiral products of high molecular complexity in high yields and with excellent enantioselectivities. Unlike organometal catalysts, organocatalysts do not contaminate products with toxic heavy metals and this is important in terms of medicinal chemistry. However, in some cases they may be responsible for hardly separable and potentially dangerous organic impurities. To facilitate product purification and recovery of precious chiral catalysts, immobilized forms of organocatalysts tagged to polymers or ionic groups have been designed and organocatalytic reactions have been carried out in so called neoteric green solvents, particularly in ionic liquids (IL), water and liquid or supercritical (sc) carbon dioxide. In these systems a catalyst and a product are located in different phases during the catalytic process and/or the working-up step. We developed highly efficient enantioselective cross-aldol reactions between various carbonyl compounds in the presence of proline or prolinamide-derived organocatalysts in the IL and/or aqueous environment. An original method for adapting -amino acid-sourced IL-supported chiral organocatalysts to the aqueous medium via an incorporation of long-chain alkyl groups and hydrophobic anions into their molecules and by performing asymmetric reactions in reagents/water two-phase systems was elaborated. Corresponding aldol products were obtained in high yields and with extremely high anti -diastereo- (dr up to 98 : 2) and enantioselectivities (ee up to 99%) under proposed conditions. After product isolation, the remaining catalyst-water heterogeneous system could be reused up to 15 times without a decrease of product yield and selectivity of the reaction. 1 Carbon acids, in particular malonates, malononitrile, and anthranone, appeared to react enantioselectively with nitroalkenes in the presence of tertiary amine/thiourea-derived bifunctional organocatalyst in liquid C 2 as a green substitute of toxic organic solvents to afford the respective Michael adducts in moderate to high yields and with enantioselectivities of up to 92% ee. 2 The first green asymmetric organocatalytic reaction in sc-c 2, namely, a bifunctional squaramidecatalyzed addition of diphenylphosphite to α-nitroalkenes to afford β-nitrophosphonates in high yields and with ee-values of up to 94% was elaborated. 3 In this way, the most active (R)-enantiomer of the therapeutically useful GABA B receptor agonist baclofen, a key precursor of the chiral anticonvulsant, pregabalin, and both enantiomers of pharmacologically important β-amino phosphonic acid derivatives were synthesized. A significant potential of the supercritical extraction for product isolation and catalyst recovery, which completely eliminates the use of organic solvents during the working-up procedure, was demonstrated. The work was financially supported by the Russian Foundation of Basic Research (projects , and ). 1. D.E. Siyutkin, A.S. Kucherenko, S.G. Zlotin. In Comprehensive Enantioselective rganocatalysis: Catalysts, Reactions, and Applications, ed. by P.I. Dalco, Wiley-VCH, 2013, v. 2, p A.G. igmatov, I.V. Kuchurov, D.E. Siyutkin, S.G. Zlotin. Tetrahedron Lett., 2012, 53, I.V. Kuchurov, A.G. igmatov, E.V. Kryuchkova, A.A. Kostenko, A.S. Kucherenko, S.G. Zlotin. Green Chem., 2014, 16,

58 IL35 MAKIG LEFI METATHESIS WRK - RECET RESULTS I RUTHEIUM CATALYSTS DESIG K.L. Grela Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon-carbon double bonds [1]. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions [1]. However, formation of substituted and crowded double bonds, decreasing the amount of metal, using metathesis in green context, etc. still remain a challenge, making industrial applications of this methodology difficult [2]. These limitations can be solved by designing new, more active and stable catalysts and catalysts that can be easier removed / recycled [3]. During the lecture a number of representative examples will be presented. Artwork Katarzyna Felchnerowska, References [1] lefin Metathesis: Theory and Practice, Grela, K. (Ed.), John Wiley & Sons, 2014 [2] Thayer, A. Chemical & Engineering ews 2007, 85 (07), 37. [3] Clavier, H.; Grela, K.; Kirschning, A.; Mauduit, M.; olan, S. P. Angew. Chem. Int. Ed. 2007, 46,

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60 ral Communications 60

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62 C1 THE FIRST CYCLPETADIEYL ICKEL CMPLEXES BEARIG A SILYL GRUP R HYDRGE SUBSTITUTED PHSPHIE CHELATIG SIDECHAI I. Werner, H. Butenschoen Institute of rganic Chemistry, Leibniz Universitaet Hannover, Hannover, Germany The only known secondary phosphine pendant cyclopentadienyl complexes are those of zirconium and hafnium, reported by Ishiyama et al. in [1] Since these complexes contain a reactive phosphorus-hydrogen bond, they were converted into the corresponding phosphide-substituted cyclopentadienyl chelate complexes. [2] Both systems were successfully applied in catalytic ethylene and styrene polymerization reactions as well as in ethylene/styrene copolymerization reactions. [3] To our knowledge, no analogous complexes of late transition metals containing a phosphorushydrogen or a phosphorus-silyl bond have so far been reported. We report on the synthesis of the first cyclopentadienyl nickel complexes 1-4 and 5, 7 bearing a silyl group and hydrogen substituted phosphine chelating sidechain, respectively. Treatment of complex 5 with SIMes induced the decomplexation of the secondary phosphane substituted tether, delivering exclusively nickel carbene complex 6. Recrystallization of complex 7 from hexane/ethyl acetate (1:1) at 30 C afforded crystals suitable for an X-ray crystal structure analysis. References: [1] T. Ishiyama, H. akazawa, K. Miyoshi, J. rganomet. Chem. 2002, 648, 231. [2] T. Ishiyama, T. Mizuta, K. Miyoshi, H. akazawa, rganometallics 2003, 22, [3] T. Ishiyama, K. Miyoshi, H. akazawa, J. Mol. Cat. A-Chem. 2004, 221,

63 C2 EXPADED RIG -HETERCYCLIC CARBEE TRASITI METAL CMPLEXES. SYTHESIS, STRUCTURE, APPLICATIS I CATALYSIS M.S. echaev 1, A.F. Asachenko 2, P.B. Dzhevakov 2,.S. Morozov 2, G.V. Proskurin 1, P.S. Gribanov Moscow State University, Department of Chemistry, Moscow, Russia 2 - A. V. Topchiev Institute of Petrochemical Synthesis, RAS, Moscow, Russia -heterocyclic carbenes (HCs) became widely used as organocatalysts and as ligands in transition metal catalysis. Most of HC-metal complexes known to date are derived from five-membered ring imidazol-2-ylidene and imidazolin-2-ylidene type carbenes. In recent years, our group develops chemistry of 6-, 7- and 8-membered ring carbenes. Expanded ring carbenes (er-hcs) exhibit superior stereoelectronic properties in comparison with five-membered ring counterparts. Expansion of the ring leads to significant increase in donor strength and sterical hindrance. In this contribution we report our recent results on theoretical calculations of electronic structure and ligand properties of er-hcs; efficient methods of synthesis of precursors and generation of free carbenes; synthesis of late transition metal (Cu, Ag, Au, Pd) complexes. It was found that er- HC complexes of palladium are highly active in Suzuki-Miyaura coupling in water, and dimerization of terminal alkynes with formation of E-enynes. Cationic gold complexes are active catalysts of addition of nucleophiles to carbon-carbon triple bonds. 63

64 C3 PALLADIUM-CATALYZED C H ALKEYLATI F AREES USIG SULFUR-CTAIIG DIRECTIG GRUPS: A CMPARATIVE STUDY K.V. Luzyanin, A.. Marjanov, V.P. Ananikov Laboratory of Cluster Catalysis, Saint Petersburg State University, Universitetsky pr. 26, Stary Petergof, , Russia Direct alkenylation of organic substrates via directing-group assisted functionalization of the CH bond has emerged as a valuable tool for creation of new sp 2 -sp 2 bonds. In the contrast to the Mirozoki Heck reaction that starts from the aryl halides, this procedure works with inactivated arenes and is favorable from both economical and environmental points of view. Several types of directing groups have been evaluated in the direct alkenylation up to date, e.g., ketones and carboxylates, amides, pyridine sulfoxides and ethers, and thioethers. Among them, functionalization of sulfur-containing compounds (Scheme 1), i.e. pyridine thioesters and sulfoxides, as well as structurally related benzylic thioethers (in those, sulfur moiety plays a role of a directing group) attracts rapidly growing attention. n the one hand, functionalization of such compounds leads to interesting derivatives containing both alkene and sulfur functions, while, on the other hand, sulfurbased directing groups in these species can be easily removed after reaction from the resulting products without compromising other functionalities. 1 3 Scheme 1. Direct alkenylation of arenes using sulfur-containing directing groups. In the current report, we summarize data accumulated up to date regarding direct CH-alkenylation of sulfur-containing organic compounds. A particular emphasis is given to the evaluation of the assistance provided by different sulfur-containing directing groups in comparison to other common directing moieties known to be employed for this purpose. Acknowledgements: This work has been partially supported by the Saint Petersburg State University (research grant from Laboratory of Cluster Catalysis), and the Russian Fund for Basic Research (grant ). References 1. García-Rubia, A.; Fernández-Ibánez, M. A.; Gómez Arrayás, R.; Carretero, J. C. Chem. Eur. J. 2011, 17, Yu, M.; Xie, Y.; Xie, C.; Zhang, Y. rg. Lett. 2012, 14, Zhang, X.-S.; Zhu, Q.-L.; Zhang, Y.-F.; Li, Y.-B.; Shi, Z.-J. Chem. Eur. J. 2013, 19,

65 C4 I PURSUIT F A VEL IMIDATE-BASED SALE-TYPE LIGAD CLASS J. Van Der Eycken 1, P. Janssens 1, T. oel Ghent University, Department of rganic Chemistry 2 - Eindhoven University of Technology, Department of Chemistry and Chemical Engineering, Micro Flow Chemistry & Process Technology An increasing ecological awareness and global competitiveness have challenged the chemical industry towards a higher level of sustainability through innovation and technology. In research, the majority of topics on sustainable process development deals with catalysis. [1] Furthermore, in organic synthesis, transition metal catalysis already plays a vital role in the synthesis of biologically active compounds. [2] H H H H H H H H L 1 L 2 Bisimidate ligand L 2 shows striking similarities with Salen ligands (L 1 ). We reasoned that this [3-5] could open new opportunities for our already well-established imidate ligand family. evertheless, the applicability of this ligand in the Mn V -catalyzed asymmetric epoxidation reaction turned out to be more complicated than expected. In this communication, the search towards an effective novel imidate-based Salen-type ligand class will be discussed from a ligand design point of view. References [1] Dichiarante, V.; Ravelli, D.; Albini, A. Green Chem. Lett. Rev. 2010, 3, 105. [2] a) oyori, R Angew. Chem. Int. Ed. 2002, 41, b) Busacca, C.A.; Fandrick, D.R.; Song, J.J.; Senanayake, C.H. Adv. Synth. Catal. 2011, 353, [3] a) oël, T.; Bert, K.; Van der Eycken, E.; Van der Eycken, J. Eur. J. rg. Chem. 2010, 21, b) Bert K., oël T., Van der Eycken J., rg. Biomol. Chem., 2012, 10, c) oël, T., Bert, K., Janssens, P. and Van der Eycken, J. (2012) Chiral Imidate Ligands: Synthesis and Applications in Asymmetric Catalysis, in: Innovative Catalysis in rganic Synthesis: xidation, Hydrogenation, and C-X Bond Forming Reactions (ed P. G. Andersson), Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: / ch14. 65

66 C5 ITRALKAES I PPA AS EW REAGETS FR DIRECT METAL- FREE AMIATI F AREES A.V. Aksenov 1,.A. Aksenov 1, I.V. Aksenova 1, M. Rubin 2, D.A. Aksenov Department of Chemistry, orth Caucasus Federal University, Stavropol, Russian Federation 2 - Department of Chemistry, University of Kansas,Lawrence, USA Aromatic amines represent an important class of organic compounds. Many of them demonstrate important biological activities. Various multi-step methods for preparation of these compounds have been developed, including electrophilic nitration/reduction sequence, Schmidt and Beckmann rearrangements, etc. The most appealing methods, however, are those that allow for direct introduction of an amino-group to a non-substituted arene over a single step. Direct electrophilic acetamidation of arenes 2 with primary nitroalkanes 1 in polyphosphoric acid (PPA), recently developed in our laboratories can be viewed as an example of such an approach. R 1 + P P A R + P H... R 3 R 2 2 R 4 R 1 R=Me, Pr, Ph, Bn; R 1, R 2, R 3, R 4 =H, Me, H, Me, CH. Benzene and arenes with electron-donating substituents can be engaged in this reaction. Electron deficient arenes are inert. The process is highly selective, the electrophilic attack is always directed to para-position with respect to a substituent already present in the ring. Anthracene 4 and indole 5 were successfully involved into the acetamidation reaction. In reaction of dibenzo-18-crown-6 ether monoacetamide was formed along with quite a large amount of bisacetamination isomeric products. The reaction involving secondary nitroalkanes is also interesting. Since the nitroso compound 4, resulting from electrophilic attack to the aromatic ring, is not able to isomerize oxime, it attacks a second molecule of arene. After rearrangement this leads to the formation of diarylamines 5: R 3 R 2 R 4 R 1 R H P... R 3 R 2 R 4 R 1 3 H R % R 1 R 2 P P A R 1 R P 2 H... H - H + R 1 R 2 R 1 R 2 R 1 R 2 H R 1 -P P A H R 1 - H P 2 H... 2 R 1 R 2 H R 1 R % R 1, R 2 =H, Me, Me, CH A novel protocol for direct and regioselective metal-free acetamination and amination of arenes in reactions with primary and secondary nitroalkanes in polyphosphoric acid media was developed. A new preparative approach to 5-aminoindoles and diarylamines employing this reaction was demonstrated. This work was carried out with financial support from the Russian Foundation Basic Research (grants a and mol_a) 4 R 2 R 2 66

67 C6 URTRPIE ISMER (1,4,6,10-TETRAAZAADAMATAE). MLECULAR SIMPLICITY AD MLECULAR CMPLEXITY F HETERADAMATAE CAGE A.Yu. Sukhorukov, A.. Semakin, I.S. Golovanov, S.L. Ioffe, V.A. Tartakovsky.D. Zelinsky Institute of rganic Chemistry, Moscow, Russia For more than 100 years, heteroadamantanes have been objects of rapt attention for fundamental and applied chemistry. These cage polycyclic systems represent interest not only due to their unique properties, but also as convenient models for the study of basic problems dealing with structure and reactivity of organic compounds. Among many heteroadamantanes, 1,3,5,7-tetraazaadamantane (urotropine), which was first obtained by A. Butlerow in 1859, plays, probably, the most important role from an applied point of view. Urotropine is widely used in medicine, polymer production, food industry, as well as organic synthesis, coordination chemistry and MFs design. This simplest T d -symmetrical 1,3,5,7-tetraazaadamantane is the only known representative of the class of tetraazaadamantanes. In this context the possibility of existence of other tetraazaadamantanes isomeric to urotropine represents considerable fundamental interest. The present report deals with the first synthesis of 1,4,6,10-tetraazaadamantane ( isourotropine ), the C 3v -symmetrical structural isomer of urotropine, and a series of its derivatives (see Figure). X- Ray and quantum-chemical studies demonstrate remarkable distinctions in structures of urotropine and isourotropine cages, probably, arising from different types of lp( eq ) * C interactions in these heterocage systems. Since substitution at bridge and bridgehead nitrogen atoms can be easily installed, 1,4,6,10-tetraazaadamantane can be considered as a new rigid multivalent (3+1) scaffold for the design of complex functional molecules and materials. Acknowledgement The financial support from RFBR (grant a) and Russian President s Council for Grants (grant MK ) is greatly acknowledged. 67

68 C7 PALLADIUM-CATALYZED CRSS-CUPLIG REACTI F ALCHL WITH ARYL CHLRIDE THRUGH C-C BD ACTIVATI C.-H. Jun, H.-S. Park, D.-S. Kim Yonsei University, Department of Chemistry, Seoul, South Korea The C-C bond activation is one of challenging subjects in organometallic chemistry. 1 Especially catalytic version of C-C bond activation has been recently achieved by chelation assisted transition metal catalyst, consisted of Rh(I) and 2-amino-3-picoline. 2 During the course of our studies on these types of C-C bond activation, we found decarbonylative esterification of aliphatic alcohol with aryl chloride by palladium metal as shown below. For example, when the reaction of chlorobenzene and 1-naphtylethanol was carried out at 150 o C under Pd/C and af base, a mixture of three products, 1-naphtylethyl benzoate ester, benzene, and 1-methylnaphthalene, was obtained in reasonable yields. The reaction mechanism is proposed as follows. The reaction proceeds through several consecutive reactions. Initially, primary alcohol is oxidized by aryl chloride to aldehyde with formation of aryl- H under palladium catalyst. Aldehyde is decarbonylated by Pd to generate alkane and (C)Pd. The intermediate (C)Pd is oxidatively added to aryl chloride to form acyl-pdcl complex, which reacts with alcohol to give ester compounds. In this reaction, reactivity of substrate should be well balanced. The reactivity of chloroarene is suited for this purpose since other aryl halide such as bromobenzene and iodobenzene did not show any reactivity in this reaction. This result is quite interesting since aryl chloride is least reactive for common C-C bond coupling reaction while aryl iodide is very reactive. The reaction works well with aryl chloride. ne of merits in this protocol is that carbonylation proceeds without using toxic C gas, and C source is non-toxic alcohol. More detailed mechanistic studies using 13 C-enriched or deuterated alcohol will be discussed. References 1. Jun, C. -H. Chem. Soc. Rev. 2004, 33, Park, Y. J.; Park, J. -W.; Jun, C. -H. Acc. Chem. Res. 2008, 41,

69 C8 RADICAL-CATIS F ACETYLEE CMPUDS I CARB- CARB BD FRMIG REACTIS A.V. Vasilyev Saint Petersburg State Forest Technical University, Institutsky per. 5, Saint Petersburg, , Russia; Saint Petersburg State University, Institute of Chemistry Radical-cations of acetylene compounds A, generated under oxidation of alkynes I in systems Pb 2 -strong acid (CF 3 C 2 H, HF, HS 3 F), are key reaction intermediates in various new carboncarbon bond forming processes [1-6]. Depending on structure, the species A lead to formation of a variety of products II-VII. When substituents X are moderate electron acceptors C 2 R, CAr, CR, P(Et) 2, trans-ethenes II are stereoselectively formed. In case of stronger acceptors, furan derivatives III (X = CCF 3, СОC 2 Et), or diketones IV (X = CF 3 ) are formed. In different acidic systems radical-cations of diarylacetylenes (X = Ar) give unsaturated diketones V (in CF 3 C 2 H), butadiene difluiorides VI (in HF) or dichlorides VII (in HS 3 F, followed by quenching in HCl aqua.,conc. ). The last ones are electro-cyclically converted into naphthalenes VIII. R Cl Ar Ar Ar X = Ar C C 1. H + =HS 3 F; 2. HCl Cl C C Cl Ar Ar X = Ar VII H + = HF F Ar Ar VIII Ar C C Ar C C Ar Ar VI F Ar C C X I X = C 2 Alk, Pb 2 /H + -e CAr, CMe, P(Et) 2 Ar C C A X X = Ar H + = CF 3 C 2 H Ar Ar C C Ar C C Ar V Ar X C C X = CCF 3, CC 2 Et C C X II X Ar C C C Ar Ar C C Y III Y = CF X = CF 3, 3 C 2 Et F 3 C CF 3 H C C H Ar C C Ar IV [1] Vasilyev A.V., Rudenko A.P. Russ. J. rg. Chem. (in Engl.), 1997, V.33, P [2] Shchukin A.., Vasilyev A.V., Fukin G.K., Rudenko A.P. Russ. J. rg. Chem. (in Engl.), 2007, V.43, P [3] Vasilyev A.V., Aristov S.A., Fukin G.K., Kozhanov K.A., Bubnov M.P., Cherkasov V.K. Russ. J. rg. Chem. (in Engl.), 2008, V.44, P [4] Vasilyev A.V., Shchukin A.., Walspurger S., Sommer J. Eur. J. rg. Chem., 2008, [5] Vasilyev A.V., Rudenko A.P. Russ. J. rg. Chem. (in Engl.), 2010, V.46, P [6] Alkhafaji H.M.H., Vasilyev A.V., Ryabukhin D.S., Rudenko A.P., Muzalevskiy V.M., enajdenko V.G. Russ. J. rg. Chem. (in Engl.), 2013, V.49, P

70 C9 ACTIVATI F Ru-BASED LEFI METATHESIS CATALYSTS A. Poater 1, L. Cavallo Institut de Quimica Computacional i Catаlisi and Departament de Quimica, Universitat de Girona, Campus de Montilivi, E Girona, Catalonia, Spain 2 - Kaust Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal , Saudi Arabia In recent years olefin metathesis catalyzed by -heterocyclic carbene ruthenium complexes has attracted remarkable attention as a versatile tool to form new C=C bonds.[1] The last developed (pre)catalysts show excellent performances, and this achievement has been possible because of continuous experimental and computational efforts to understand the laws controlling the behavior of these systems. This perspective talk rapidly traces the ideas and discoveries that computational chemistry contributed to the development of these catalysts, with particular emphasis on catalysts presenting a -heterocyclic carbene ligand. Specifically, one of the most important challenges in ruthenium-catalyzed olefin metathesis is to increase the stability of the catalysts under reaction conditions and this hopefully without loss of activity. Special interest has been addressed to study the activation of the second-generation Grubbs catalysts, which has clarifier either a dissociative or an interchange mechanism is feasible.[2] Although, in the solid state, most ruthenium-based olefin metathesis catalysts are stable to oxygen and moisture, in solution decomposition usually occurs readily. Understanding the decomposition routes of catalysts is extremely important as any insight gained in this area can guide catalyst design efforts, to participate then in the synthesis of drugs.[3,4] Furthermore, new challenging projects plan to modify the structure of the HC ligands, or replace this ligand by alkylidene ligands, and even the substitution of the metal is a goal, moving to more environmentally friendly metals. [1] G. C. Vougioukalakis, R. H. Grubbs, Chem. Rev. 110, 1746 (2010). [2] C. A. Urbina-Blanco, A. Poater, T. Lebl, S. Manzini, A. M. Z. Slawin, L. Cavallo, S. P. olan, J. Am. Chem. Soc. 135, 7073 (2013). [3] S. Manzini, C. A. Urbina-Blanco, A. Poater, A. M. Z. Slawin, L. Cavallo, S. P. olan, Angew. Chem. Int. Ed. 51, 1042 (2012). [4] S. Manzini, A. Poater, D. J. elson, L. Cavallo, S. P. olan, Chem. Sci. 5, 180 (2014). 70

71 C10 CHEMICAL REACTIVITY I PRTEIS AD WATER: QM/MM MD ISIGHTS IT EFFECTS F LCAL STRUCTURAL EVIRMETS BD CLEAVAGE Y. Zhao, B.J. Wang, R.B. Wu, Z.X. Cao Department of Chemistry, Xiamen University, Xiamen , China Water and proteins play a quite important role in chemical and biological processes. In past few years, we carried out a systematic investigation on the effect of local structural environments on reactivity towards hydrolysis, C-, C-, and C-H bond cleavages in proteins and water. Using Born-ppenheimer ab initio QM/MM MD simulations, a state-of-the-art approach to simulating enzymes, we have investigated the structural features of zinc enzymes, nucleoside hydrolase, and deaminase and plausible enzymatic mechanisms. The molecular complexity of active domain in enzyme and roles of conserved residues and protein environments in enzymatic catalysis have been explored. In particular, the different coordination modes and fast ligand exchanges of zinc coordination has been suggested to be one key catalytic feature of the zinc ion, and the chelation mode of hydroxamate with the zinc ion in HDACs is modulated by water access to the linker binding channel. This new insight into the interplay between the linker binding and the zinc chelation emphasizes its importance for the development of new class-iia-specific HDAC inhibitors. ur calculations indicate that the reliable theoretical treatment on the water-mediated proton transfer and most hydrolysis reactions of carbonyl compounds, such as aldehydes, ketones, esters, amides, the carboxylic acids, and their derivatives, requires use of the large basis set and suitable cluster-continuum model. The effects of solvent and structural modification on hydration and hydrolysis of carbonyl compounds have been discussed. Acknowledgements. This work was supported by the ational Science Foundation of China ( and ) and the Ministry of Science and Technology (2011CB808504). References 1. Chen, H. Ge, J Xu, Z Cao, and R Wu, Biochim. Biophys. Acta 2013, 1834, R Wu, W Gong, T Liu, Y Zhang, and Z Cao, J. Phys. Chem. B , B Wang and Z Cao, Chem. Eur. J , B Wang and Z Cao, Angew. Chem. Int. Ed. 2011, 50, R Wu, Z Lu, Z Cao, and Y Zhang, J. Am. Chem. Soc. 2011, 133, Y Zhao, Chen, R Wu, and Z Cao, 2013, submitted. 71

72 C11 MECHAISM F ITRAMLECULAR HECK REACTI BY DESITY FUCTIAL THERY A. Ayyappan, D. Yogeswara Rao Indian Institute of Technology Kharagpur, Department of Chemistry, West Bengal India Heck Reaction, the palladium-catalyzed C-C coupling between aryl halides or vinyl halides and activated alkenes in the presence of a base, is widely used in syntheric chemistry. Intramolecular version of Heck reaction is a route to the generation carbocycles that are scaffolds of many important natural products and biologically active molecules. Although the mechanism of intermoelcular Heck reactions is well established, the intramelecular variant is not analyzed in detail for its mechanistic features. Using Density Functional Theory computations, we have explored the the catalytic cycle of intramolecular Heck reaction, that involves oxidative addition, migratory insertion (cyclization) and β-hydride elimination (See Figure). Two pathways were analyzed, which differ in their initial coordination face (Re or Si) of the terminal alkene with the metal centre. The choice of pathway is not evident from free energy profile, because one of the pathways have higher barrier for oxidative addition, the other requires high activation energy for β-hydride elimination. Detailed analysis of the mechanism will be presented. In addition, our attempts to analyze such complex reaction mechanisms by kinetic simulations will be discussed. Figure: Catalytic cycle for the intramolecular Heck reaction. 72

73 C12 CYCLDIMERIZATIS F DR-ACCEPTR CYCLPRPAES: SHRTCUT APPRACH T CMPLEX RIG SYSTEMS E.M. Budynina,.A. Ivanova, A.. Chagarovskiy, I.V. Trushkov Moscow State University, Department of Chemistry, Moscow, Russia Cyclodimerization is among the most challenging and fascinating reactions providing significant increase in structural complexity within one operation step in highly stereoselective manner and occurring both in vivo and in vitro. In organic synthesis, among typical substrates that undergo cyclodimerizations, donor-acceptor (DA) cyclopropanes, 1 in which small ring is vicinally activated with donor and acceptor groups, occupy a special place. Currently, at least dozen types of Lewis acid-triggered cyclodimerization of such DA cyclopropanes as 2-(het)aryl-cyclopropane-1,1- diesters are known which open rapid approaches to diverse ring compounds, including complex polycyclic and bridged molecular systems. 2 Recently, on basis of (3+3)-cyclodimerizations of 2-arylcyclopropane-1,1-diesters we developed straightforward and efficient approaches to 1,4-diarylcyclohexanes, 1-aryltetralins or 9,10- dihydroanthracenes. 2a (3+2)-Cyclodimerizations of similar cyclopropanes provide an easy access to diarylcyclopentanes 2b,c and arylindanes. 2d Cyclodimerizations of 3- and 4-indolyl-derived DA cyclopropanes allows for the construction of complex tetra- and heptacyclic cores of bisindoles. 2e 1. a) Reissig, H.-U.; Zimmer, R. Chem. Rev. 2003, 103, 1151; b) De Simone, F.; Waser, J. Synthesis 2009, 3353; c) Mel nikov, M.Ya.; Budynina, E.M.; Ivanova,.A.; Trushkov, I.V. Mendeleev Commun. 2011, 21, 293; d) Schneider, T.S.; Kaschel, J.; Werz, D.B. Ang. Chem. Int. Ed. 2014, 53, /anie a) Ivanova,.A.; Budynina, E.M.; Chagarovskiy, A..; Trushkov, I.V.; Melnikov, M.Ya. J. rg. Chem. 2011, 76, 8852; b) Chagarovskiy, A..; Ivanova,.A.; Budynina, E.M.; Trushkov, I.V.; Melnikov, M.Ya. Tetrahedron Lett. 2011, 52, 4421; c) ovikov, R.A.; Korolev, V.A.; Timofeev, V.P.; Tomilov, Yu.V. Tetrahedron Lett. 2011, 39, 4996; d) Ivanova,.A.; Budynina, E.M.; Skvortsov, D.A.; Limoge, M.; Bakin, A.V.; Chagarovskiy, A..; Trushkov, I.V.; Melnikov, M.Ya. Chem. Commun. 2013, 49, 11482; e) Ivanova,.A.; Budynina, E.M.; Chagarovskiy, A..; Rakhmankulov, E.R.; Trushkov, I.V.; Semeykin, A.V.; Shimanovskii,.L.; Melnikov, M.Ya. Chem. Eur. J. 2011, 17, 11738; f) ovikov, R.A.; Tarasova, A.V.; Korolev, V.A.; Timofeev, V.P.; Tomilov, Yu.V. Ang. Chem. Int. Ed. 2014, 53, 3187; g) ovikov, R.A.; Tomilov, Yu.V. Helv. Chim. Acta 2013, 96,

74 C13 USIG RIG STRAI RELEASE FR ALLEVIATI F TRASAULAR STRAI: SMALL RIG-TEMPLATED SYTHESIS F MEDIUM HETERCYCLES M. Rubin, M. Rubina, A. Edwards, P. Ryabchuk University of Kansas, Department of Chemistry A highly efficient diastereocenvergent reaction of bromocyclopropanes with various nucleophiles have been recently developed in our laboratories. 1-7 This reaction involves a base-assisted dehydrohalogenation to produce a highly reactive cyclopropene intermediate, which undergoes subsequent nucleophilic addition across the strained C=C bond. Different intramolecular modes of this reaction will be presented. Possibilities for assembly of heterocyclic scaffolds with various ring sizes, including enantiomerically pure medium heterocycles, will be demonstrated. The mechanistic aspect of this transformation and the means of controlling its diastereoselectivity will be discussed. Me H H 15-membered Me t-buk/ DMS t-buk/ THF Ph Ph 5-membered 8-membered H Ar H Me KH/THF R 8-9-membered R Br u 18-crown-6 (cat) Base/THF t-buk/ DMS t-buk/thf t-buk/ THF R" R"' R R 8-membered H Me 7-10-membered References [1] Alnasleh, B. K.; Sherrill, W. M.; Rubina, M.; Banning, J.; Rubin, M. J. Am. Chem. Soc. 2009, 131, [2] Banning, J. E.; Prosser, A. R.; Rubin, M. rg. Lett. 2010, 12, [3] Prosser, A. R.; Banning, J. E.; Rubina, M. Rubin, M. rg. Lett. 2010, 12, [4] Banning, J. E.; Prosser, A. R.; Alnasleh, B. K.; Smarker, J.; Rubina, M.; Rubin, M. J. rg. Chem. 2011, 76, [5] Ryabchuk, P.; Rubina, M.; Xu, J.; Rubin, M. rg. Lett. 2012, 14, [6] Banning, J. E.; Gentillon, J.; Ryabchuk, P.; Prosser, A. R.; Rogers, A.; Edwards, A.; Holtzen, A.; Babkov, I. A.; Rubina, M.; Rubin, M. J. rg. Chem. 2013, 78, [7] Ryabchuk, P.; Edwards, A.; Gerasimchuk,.; Rubina, M.; Rubin, M. rg. Lett. 2013, 15,

75 C14 THE STRATEGY FR ATM ECMICAL REDUCTIVE ADDITI DEXYGEATI D. Chusov, P.. Kolesnikov, V.I. Maleev,.Z. Yagafarov A..esmeyanov Institute of rganoelement Compounds of Russian Academy of Sciences Herein we present the concept of using carbon monoxide for atom economical reductive addition deoxygenation without external hydrogen source [1]. We are utilizing this idea by showing that - H and C-H bonds of the reagents could be used as hydrogen source (Fig. 1). Figure 1 References: D. Chusov, B. List, Angew. Chem. Int. Ed., 2014, 53, DI: /anie

76 C15 DIUCLEAR CATALYSIS: ACCELERATED, METAL-DEPEDET RIG- PEIG PLYMERIZATI F LACTIDE E. Kirillov Universite de Rennes 1, UMR CRS, Rennes France Multinuclear olefin polymerization catalysts (incorporating several active metal centers in one and the same molecule) have recently emerged as a distinct and brand new class of molecular catalysts. 1 Implicit cooperative behavior 2 of two or more metal centers in active species of these systems can contribute to enhanced performance (with respect to mononuclear analogues) in terms of activity, chain-transfer kinetics and, also, monomers selectivity in copolymerization reactions. Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been synthesized and used in the polymerization of lactide. 3a Kinetic studies demonstrated that the dialuminum precursor (Scheme 1) provides a more favorable reaction pathway in terms of activation free energy than that of directly related monoaluminum systems. 3b o similar trend was observed with the corresponding diindium / monoindium systems, which was attributed to a dissimilar RP mechanism. Details of the mechanisms and key factors of the dinuclear catalysis will be discussed. Scheme 1. A dinuclear aluminum system enables a 5-to-10 fold boost in activity when compared to its monoaluminum analogues. 1. Delferro, M.; Marks, T. J. Chem. Rev. 2011, 111, Bratko, I.; Gómez, M. Dalton Trans., 2013, 42, (a) ormand, M.; Roisnel, T.; Carpentier, J.-F.; Kirillov, E. Chem. Commun. 2013, 49, (b) ormand, M.; Dorcet, V.; Kirillov, E.; Carpentier, J.-F. rganometallics 2013, 32,

77 C16 RECET METHDLGICAL DEVELPMETS FR THE QUATUM CHEMICAL STUDY F CMPLEX SYSTEMS S. Irle agoya University, Department of Chemistry, agoya, Japan The structural complexity of molecular clusters increases with size due to the associated, rapidly growing configuration space. Two examples are realized in i) the transition from molecular to bulk systems, and ii) in the simulation of extended biosystems. In such systems, traditional quantum chemical approaches of investigations are hampered by the vastly increasing computational cost, even considering ever-growing supercomputer capabilities. Computationally inexpensive, yet accurate schemes such as the density-functional tight-binding (DFTB) method [1] and there linear scaling versions promise here a significant advantage. We have recently engaged in developing novel methodologies for systems with increasing structural complexity, driven by motivation from experimental studies. In this presentation, we will review a) the Kick-fragment-based Kick 3 conformationally aware approach for studying molecular [2] and ionic liquid clusters with increasing size, and our implementation of the fragment molecular orbital (FM) method [3] with DFTB, called FM-DFTB, in the popular GAMESS- US quantum chemistry package [4]. The computational effort of the method scales nearly linearly with system size with a negligible pre-factor, and allows the efficient, massively-parallel quantum chemical geometry optimization and direct molecular dynamics (MD) simulations of systems containing several tens of thousands of atoms, in particular when fragments consist of units with less than 50 atoms [5]. The method should be particularly useful to predict structures of new artificial peptides and proteins, predict enzymatic reaction pathways, estimate free energy contributions along pathways where large parts or even the entire protein including surrounding water is treated quantum chemically, and to simulate the effects of highly polarizable and/or charged solvents in explicit-solvent MD simulations. Unlike other linear scaling schemes, such as divide and conquer approaches (DC), FM-DFTB's very design allows the insightful decomposition of interaction energies between ligands and proteins in terms of electrostatics, exchange-repulsion, charge transfer, dispersion and solvent screening contributions in a straightforward manner. [1] M. Gaus, Q. Cui, M. Elstner, J. Chem. Theory Comput. 7, 931 (2011). [2] M. A. Addicoat, S. Fukuoka, A. J. Page, S. Irle, J. Comput. Chem. 34, 2591 (2013). [3] D. G. Fedorov, T. agata, K. Kitaura, Phys. Chem. Chem. Phys. 14, 7562 (2012). [4] M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki,. Matsunaga, K. A. guyen, S. Su, T. L. Windus, M. Dupuis and J. A. Montgomery, Jr., J. Comput. Chem., 1993, 14, 1347; [5] Y. ishimoto, D. G. Fedorov, S. Irle, submitted. 77

78 C17 QUATUM CHEMICAL MDELIG I STUDIES F MLECULAR MECHAISMS F EZYME CATALYSIS A.V. emukhin Chemistry Department, M.V. Lomonosov Moscow State University, Moscow, , Russia;.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia Recent results [1-3] of modeling chemical transformations in enzyme active sites using quantumbased approaches will be discussed. We apply quantum mechanics/molecular mechanics (QM/MM) approaches to compute minimum energy pathways connecting enzyme-substrate and enzymeproduct complexes. Appropriate crystal structures from the Protein Data Bank usually serve as a source of coordinates of heavy atoms to create molecular model systems. After in silico construction of a three-dimensional full-atom model, evolution of the model system along carefully selected reaction coordinates is analyzed. Several examples of such modeling will be presented. The complete cycle of chemical transformations in penicillin acylase, a unique enzyme that belongs to the recently discovered superfamily of -terminal nucleophile hydrolases, with its most specific substrate, penicillin G, leading to formation of 6-aminopenicillanic and phenylacetic acids [1] will be presented. Ketonketal transformations at the active site of matrix metalloproteinases characterized computationally [2] may be explored to propose specific inhibitors. Chemical reactions in photoreceptor proteins constitute an active field of application of QM/MM modeling; the case of BLUF domains will be discussed [3]. Simulation results of guanosine triphposphate hydrolysis (GTP) by small GTPases, icluding Ras protein, will be in focus. According to newly obtained data, the molecular events of the chemical steps upon GTP hydrolysis include: (i) cleavage of the phosphorus (P γ ) -oxygen bond in GTP upon approach of the properly aligned catalytic water molecule, producing GDP; (ii) formation of a new chemical bond between phosphorus and oxygen of water; (iii) redistribution of protons between reacting species leading to inorganic phosphate Pi. References [1] Grigorenko B.L., Khrenova M.G., ilov D.K., emukhin A.V., Švedas V.K. Catalytic Cycle of Penicillin Acylase from Escherichia coli: QM/MM Modeling of Chemical Transformations in the Enzyme Active Site upon Penicillin G Hydrolysis // ACS Catal V. 4. P [2] Khrenova M.G., emukhin A.V., Savitsky A.P. Computational Characterization of Ketone- Ketal Transformations at the Active Site of Matrix Metalloproteinases // J. Phys. Chem. B V P [3] Khrenova M.G., emukhin A.V., Domratcheva T. Photoinduced Electron Transfer Facilitates Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light Sensors // J. Phys. Chem. B V P

79 C18 EXCITED STATES AD MLECULAR ITERACTIS I PRTEIS AD SLUTIS J.H. Hasegawa Catalysis Research Center, Hokkaido University, Sapporo, Japan Solvatochromism and fluorescent solvatochromism are well-known phenomena, and there are rich accumulations in experimental publications. Color tuning in proteins, such as human color vision and fluorescent proteins, could be also classified to solvatochromism but with a specific environment where anisotropic molecular interactions play important roles. We have studied biological color tuning with the SAC-CI/MM calculations in which MM description was adopted for the environmental effect. This classical description for the environment works very well for explaining the color tuning mechanisms. In some cases, however, environmental electronic structure effect becomes important. To investigate the origin of the QM effect, we propose a scheme based on the wave function theory with a M localization scheme. The role of the environmental electronic effect was analyzed in terms of amino acids orbital delocalizations, excitonic interactions, excited-state polarization, and dispersion interactions. In the presentation, we would show some results of pilot applications. 79

80 C19 CATIIC GLD-CATALYZED HETERAULATIS E.V. Van Der Eycken University of Leuven (KU Leuven), Department of Chemistry, Leuven, Belgium Gold catalysis is one of the fast growing research topics of modern organic chemistry. In this context, gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted much attention due to the selective and efficient activation of the C-C triple bond towards a wide range of nucleophiles. Moreover, the combination of multicomponent reactions with gold catalysis, gives access to complex molecular architectures in few steps, as compared to traditional multistep processes. We will comment on our recent findings in this field. A concise route to indoloazocines 1 via a sequential Ugi/gold-catalyzed intramolecular hydroarylation 2 will be presented. A diversityoriented approach to spiroindoles via a post-ugi gold-catalyzed diastereoselective domino cyclization 3 will be described (Scheme), as well as a regioselective approach for the synthesis of pyrrolopyridinones and pyrroloazepinones employing a gold(i)/platinum(ii) switch. 4 R 1 R 3 H 2 R 3 C i) Ugi-4CR + R 5 ii) "cationic gold", rt R 1 CH R 2 H R 2 R 4 R 5 R 4 (+/-) 13 examples up to 80% yield References: 1. Synthesis of Azocino[5,4-b]indoles via Au-Catalyzed Intramolecular Alkyne Hydroarylation, V. A. Peshkov,. P. Pereshivko, E. V. Van der Eycken, Adv. Synth. Cat., 354, , Concise route to indoloazocines via a sequential Ugi/gold-catalyzed intramolecular hydroarylation, S. G. Modha, D. D. Vachhani, J. Jacobs, L. Van Meervelt, E. V. Van der Eycken, Chem. Commun., 48 (52), , Diversity-riented Approach to Spiroindolines: Post-Ugi Gold-Catalyzed Diastereoselective Domino Cyclization, S. G. Modha, A. Kumar, D. D. Vachhani, J. Jacobs, S. K. Sharma, V. S. Parmar, L. Van Meervelt, E. V. Van der Eycken, Angew. Chem. Int. Ed., 51, , Gold(I) and Platinum(II) switch: A post-ugi intramolecular hydroarylation to pyrrolopyridinones and pyrroloazepinones, S. G. Modha, A. Kumar, D. D. Vachhani, S. K. Sharma, V. S. Parmar, E. V. Van der Eycken, Chem. Comm., 48, ,

81 Selectivity to cis-isomer, % Selectivity to alkene, % C20 Pd-SUPPRTED BIMETALLIC CMPSITIS FR STERESELECTIVE LIQUID PHASE SEMI-HYDRGEATI F DIPHEYLACETYLEE I.S. Mashkovsky 1, A.V. Sergeeva 1,.V. Turova 1, M.. Vargaftik 2,.Yu. Kozitsyna 2, A.Yu. Stakheev Zelinsky Institute of rganic Chemistry RAS, Moscow, Russia 2 - Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia This study was focused on the development of the efficient catalyst for selective semihydrogenation of internal alkene. Diphenylacetylene (DPA) was used as a model compound. The catalytic compositions based on Pd-Zn, Pd-Co, Pd-i were investigated. The samples were prepared via two techniques: (1) on the basis of palladium acetate heterobimetallic complexes as precursors and (2) using traditional co-impregnation by individual metal salts. It was found that the systems based on bimetallic acetate complexes exhibited a substantial increase in selectivity to alkene and cis-isomer formation at high conversion of the parent alkyne (DPA), albeit at the expense of some decrease in the activity. The detailed physicochemical study with TEM-EDS, SEM-EDS, EXAFS and IR-spectroscopy reveals that the use of heterobimetallic acetate complex as a precursor allows us to avoid metallic phase segregation during the reduction treatment of the catalyst, which ensures high homogeneity of bimetallic particles and leads to enhanced selectivity. Financial support was provided by RFBR foundation, grants # , %Pd-0.53%Co/Al %Pd-0.53%Co/Al %Pd-0.53%i/Al %Pd-0.53%i/Al %Pd-0.52%Zn/Al %Pd-0.52%Zn/Al %Pd/Al H H 0.93%Pd/Al H H + H H DPA conversion, % DPA conversion, % Рис. 1 Dependency of selectivity to cis-isomer and alkene on DPA conversion for Pd/Al 2 3 catalyst modified with Co, Zn and i in liquid phase DPA hydrogenation. 81

82 C21 DESIG F ASTRUCTURES THE BASIS F TW PHARMACPHRIC FRAGMETS - FULLEREE AD PIPERIDIE DERIVATIVES G.V. Grishina, I.S. Veselov, I.V. Trushkov M. V. Lomonosov Moscow State University, Department of Chemistry This communication is described the creation of a new nanobiosystems with high antivirus potential based on the two pharmacophoric fragments - derivatives of fullerene C60 and piperidine ligands. Design of nanoadditive on the basis of two pharmacophoric fragments - functional derivatives of trans-3,4-dihydroxypiperidine and organically modified by fullerene C60 can be a very promising bioactive substances. Such a perspective is related to using, first, as ligands several trans-3,4- dihydroxylated piperidines already demonstrated anti-hiv activity, and secondly, the uniqueness of fullerene spheroid significantly reduce the toxicity of biologically active adducts. We believed that binding of two biologically active units in the same system will be very useful and promising. Y X Me Y X CEt 1: X=H, Y=H 2: X=Y=H 3: X=HR, Y=H 4 Monoadducts 1-4 have obtained by the Benguel and Prato reactions, respectively, and have since received 12 new fullerene adducts based on the derivatives of the trans-3,4-dihydroxypyridine and trans-4-amino-3-hydroxypiperidines. Isolation, and identification of these adducts were made using column and preparative chromatography on silica gel, structure and stereochemistry were established with the involvement required in each case, spectral methods, including mass spectrometry and МАLDI, X-ray analysis and 1 H, 13 C MR. The main difficulty in undertake researches consisted of significant differences reactivity due to high lipophilicity derivatives of fullerene and high hydrophilicity piperidine ligands. To reduce this difference, we have modified both fragments introduction to piperidine ligands and/or in the molecule organically modified fullerenes functions and/or linkers, which facilitated further obtaining of target adducts. For some samples of adducts managed to get soluble in alcohol salts. A very important factor has been the elucidation of the impact of structural and stereochemical factors on possible synergies in the adduct investigation. Target adducts are a new type of nanostructures for medical chemistry with great pharmacological potential. 82

83 C22 CHIRASAC STUDY CHIRAL SPECTRSCPY AD PHTBILGY H. akatsuji, T. Miyahara Quantum Chemistry Research Institute (QCRI), 1-36 Goryo-ohara, ishikyo-ku, Kyoto , Japan Weak interactions of molecules with solvents and/or environments are of crucial importance in material science and biology, but rather difficult to investigate quantitatively. Circular dichroism (CD) spectra reflect sensitively the conformational structures of chiral molecules, their (weak) interactions with solvents and/or proteins, etc. The SAC-CI method gives their CD spectra very reliably. From this fact, the SAC-CI method is a useful tool to investigate the conformational geometries of chiral molecules, their interactions with environments, etc by comparing their experimental and SAC-CI theoretical CD spectra. We initiated a systematic molecular technology, called ChiraSac (Chirality + SAC-CI) project (see Figure 1) by using the SAC-CI code and other highly reliable and useful codes on GAUSSIA suit of programs [1]. We have already applied this project successfully to several topics of chiral spectroscopy and photobiology [2-4]. We will present here conformational dependence of α-hydroxyphenylacetic Acid and similarities and differences between RA and DA, etc, as some recent applications of ChiraSac to chiral spectroscopy and photobiology. References: [1] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B Mennucci,. G. A. Petersson, et al., Gaussian 09, Gaussian, Inc., Wallingford, CT, [2] Circular Dichroism Spectra of Uridine Derivatives: ChiraSac Study, Tomoo Miyahara, Hiroshi akatsuji, and Takehiko Wada, J. Phys. Chem. A 118, (2014). [3] Conformational Dependence of the Circular Dichroism Spectrum of α-hydroxyphenylacetic Acid: A ChiraSac Study, Tomoo Miyahara and Hiroshi akatsuji, J. Phys. Chem. A 117, (2013). [4] Helical Structure and Circular Dichroism Spectra of DA: A Theoretical Study, T. Miyahara, H. akatsuji, and H. Sugiyama, J. Phys. Chem. A. 117, (2013). 83

84 C23 A DFT AALYSIS THE ELECTRIC PRPERTIES F METHYLAMMIUM LEAD IDIDE PERVSKITE K. Yamashita 1, G. Giorgi 1, J. Fujisawa 2, H. Segawa Department of Chemical System Engineering, The University of Tokyo, Japan 2 - Research Center for Advanced Science and Technology, The University of Tokyo,Japan Methylammonium (MA) lead iodide perovskite (CH 3 H 3 PbI 3 ) plays an important role in light absorption and carrier transport in efficient organic inorganic perovskite solar cells [1]. In my talk, the first theoretical estimation of effective masses of photocarriers and the role of MA cation in CH 3 H 3 PbI 3 will be discussed. Spin-polarized DFT calculations have been performed with the generalized gradient approximation. From the charge density of the two-fold degenerate states ((a) and (b)) of CBM and those ((c) and (d)) of VBM, one can see that photogenerated electrons around CBM and holes around VBM exist separately, results related to the ambipolar transport nature of the material. Effective masses of photogenerated electrons and holes are estimated to be me* =0.23m0 and mh* = 0.29m0, respectively, including spin orbit coupling (SC) effects. This result is consistent with the longrange ambipolar transport property and with the larger diffusion constant for electrons compared with that for holes in the perovskite, which enable efficient photovoltaic conversion [2]. We also have focused our attention on the MA cation and studied the role it plays in the electronic/optical features of the perovskite, paying attention mainly to the iodide compound [3]. A comparison is performed between the electronic properties of MAPbI 3 organic-inorganic perovskite and those of the purely inorganic CsPbI 3. References 1. J. Bisquert, J. Phys. Chem. Lett, 4, 2597 (2013). 2. G. Giorgi, J. Fujisawa, H. Segawa, K. Yamashita, J. Phys. Chem. Lett, 4, 4213 (2013). 3. G. Giorgi, J. Fujisawa, H. Segawa, K. Yamashita, J. Phys. Chem. 118, (2014). 84

85 C24 A HYBRID MC/MD REACTI METHD WITH RARE EVET-DRIVIG MECHAISM: ATMISTIC REALIZATI F 2-CHLRBUTAE RACEMIZATI PRCESS I DMS SLUTI M. agaoka Graduate School of Information Science, agoya University, Furo-cho, Chikusa-ku, agoya , Japan; Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), Honmachi, Kawaguchi , Japan; ESICB, Kyoto University, Kyodai Katsura, ishikyo-ku, Kyoto , Japan We demonstrate a new efficient hybrid MC/MD reaction method with a rare event-driving mechanism as a practical atomistic molecular simulation of large-scale chemically reactive systems (Figure 1). Application of the method to (R)-2-chlorobutane molecules in,dimethylformamide (DMF) molecules starting in the optical pure state (100% e.e.) was found to successfully provide such an atomistic state with ~0% e.e., the expected purity of (R)- to (S)- enantiomers of the racemic mixture in chemical equilibrium [1]. This hybrid MC/MD reaction method is promising for studies of various properties in chemically reactive systems [2] and their stereochemistry as well. Figure 1. Schematic representation of the hybrid MC/MD reaction method. The curly curves represent the molecular dynamical (MD) moves in phase space following the equations of motion, while the straight lines with arrows represent the Monte Carlo (MC) moves (or transitions) of the system (right figure), whose dynamical moves would be extremely rare events. In the left figure, the configurational distribution in equilibrium p eq is proportional to the exponential factor exp[-βu] where U is the global potential function. The right figure shows regional distributions, e.g., p r eq exp[-βu r ] in region r, etc. The connecting points of the two kinds of moves (open circles) are selected according to the criteria for chemical reaction occurrence. ote that they do not represent real connections since these points correspond to almost identical states in configuration space but not in momentum space and with different configurational gradients. W r s and W s t are the transition probabilities from state r to s and from s to t, respectively [1]. [1] Masataka agaoka, Yuichi Suzuki, Takuya kamoto, orio Takenaka, Chem. Phys. Lett. 583, 80 (2013). [2]. Takenaka, Y. Suzuki, H. Sakai, M. agaoka. J. Phys. Chem. C, 118, (2014). 85

86 C25 CALIX[4]AREE-TETRATHIAFULVALEE RECEPTRS FR RECGITI F ELECTR DEFICIET GUESTS V.A. Azov, M.H. Duker, H. Schafer, D. Schluter University of Bremen For more than four decades tetrathiafulvalenes 1 (TTFs) have been extensively studied on the account of their outstanding donating properties. Due to their ability to induce reversible electrochemically-switchable processes, 1b TTFs have found their place on the forefront of supramolecular chemistry. Herein, we present synthesis and studies of a family of rationally designed redox-switchable receptors employing monopyrrolo-tetrathiafulvalenes as molecular recognition units. ur group has been long interested in synthesis and studies of tetrathiafulvalene-containing molecular architectures and their application for binding of electron-deficient molecular guests. 2 Recently, several upper rim bis-monopyrrolotetrathiafulvalene-calix[4]arene receptors were synthesized using a modular construction approach. 3a,b These compounds feature an architecture of molecular tweezers: 4 two parallel aligned electron rich TTF arms comprise a molecular recognition center. Addition of planar electron-deficient guests, such as tetracyanoquinodimethane (TCQ), to a receptor solution leads to formation of deeply-colored charge-transfer complexes, easily visible by a naked eye. Binding titrations were performed to determine the binding constants, which reached as high as M -1. Additionally, tripodal receptors comprising three TTF units attached to the 1,3,5-substituted-2,4,6-triethylbenzene scaffold, showed high affinity to pyridinium derivatives in the gas phase, as it was proven by ESI-MS experiments. 3c 1. a) J. L. Segura,. Martín, Angew. Chem. Int. Ed. 2001, 40, ; b) D. Canevet, M. Sallé, G. Zhang, D. Zhang, D. Zhu, Chem. Commun. 2009, a) V. A. Azov, R. Gómez, J. Stelten, Tetrahedron 2008, 64, ; b) M. Skibiński, R. Gómez, E. Lork, V. A. Azov, Tetrahedron 2009, 65, ; c) M. H. Düker, R. Gómez, C. M. L. Vande Velde, V. A. Azov, Tetrahedron Lett. 2011, 52, a) M. H. Düker, H. Schäfer, M. Zeller, V. A. Azov, J. rg. Chem. 2013, 78, ; b) V. A. Azov, H. Schäfer, D. Schlüter, manuscript in preparation; c) M.-L. Lieunang Watat, T. Dülcks, D. Kemken, V. A. Azov, Tetrahedron Lett. 2014, 55, For a review on topologically similar molecular tweezers, see: F.-G. Klärner, B. Kahlert, Acc. Chem. Res. 2003, 36,

87 C26 EHACED RATE AD SELECTIVITY BY CARBXYLATE SALT AS A BASIC CCATALYST I CHIRAL HC-CATALYZED ASYMMETRIC ACYLATI F SECDARY ALCHLS K. Yamada Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto , Japan Kinetic resolution of racemic secondary alcohols via enantioselective acylation is an important process in synthetic chemistry. 1 During a study to extend our previous report, 2 we found that the rates and enantioselectivities of chiral HC-catalyzed asymmetric acylation of alcohols with an adjacent H-bond donor functionality are remarkably enhanced in the presence of a carboxylate cocatalyst. The degree of the enhancement is correlated with the basicity of the utilized carboxylate. Using a cocatalyst and newly developed electron-deficient chiral HC, kinetic resolution and desymmetrization of cyclic diols and amino alcohols are achieved with extremely high selectivity (up to k rel = 218 and 99% ee, respectively) with low catalyst loading (0.5 mol %). 3 References 1 Müller, C. E.; Schreiner, P. R. Angew. Chem. Int. Ed. 2011, 50, Kuwano, S.; Harada, S.; riez, R.; Yamada, K. Chem. Commun. 2012, 48, Kuwano, S.; Harada, S.; Kang, B.; riez, R.; Yamaoka, Y.; Takasu, K.; Yamada, K. J. Am. Chem. Soc. 2013, 135,

88 C27 CFRMATIAL FLEXIBILITY, ITRA- AD ITERMLECULAR ITERACTIS AD CATALYTIC ACTIVITY F PC(sp 3 )P PICER IRIDIUM HYDRIDE CMPLEXES.V. Belkova 1, G.A. Silantyev 1,.A. Filippov 1, S. Musa 2, D. Gelman 2, L.M. Epstein 1, E.S. Shubina A.. esmeyanov Institute of rganoelement Compounds RAS, Moscow, Russia 2 - The Hebrew University of Jerusalem, Jerusalem, Israel A variety of recently developed catalysts operate via different ligand-metal cooperating mechanisms and new non-innocent ligands and their complexes keep appearing in the literature. Reversible switching between different coordination modes found in these compounds opened new practical reactivity patterns in non-oxidative (i.e. alternative to the conventional oxidative addition/reductive elimination sequence) activation and formation of polar and non-polar bonds. At that, many such systems contain stereochemically rigid pincer ligands and keep their geometry during the catalytic runs. Bifunctional dibenzobarrelene-based PC(sp 3 )P pincer iridium complex 1 is known as an efficient catalyst in acceptorless dehydrogenation of alcohols [1] and hydrogenation/hydroformylation of alkenes [2]. In order to shed light on the mechanism of the hydrogen formation/activation, we performed variable temperature IR and MR ( 1 H, 31 P) analysis of intra- and intermolecular interactions involving hydride ligand and hydroxymethyl cooperating group in 1 and its analogues. The results of the spectroscopic measurements in different media (dichloromethane, toluene, DMS, and mixed solvents) were compared with the quantum chemical (DFT /M06 and B3PW91; AIM) calculations. The data obtained imply flexibility of the dibenzobarrelene-based scaffold unprecedented for conventional pincer ligands. Both the complex 1 and its counterpart 2 prefer facial configuration of the PCP ligand with P-Ir-P angle of ca. 100º. Such geometries are dictated by stabilizing Ir interaction and differ by the mutual arrangement of the H and Cl ligands. The complexes show dynamic equilibrium between two most stable fac-isomers, which can be transformed into the meridional ones in the presence of coordinating additives (CH 3 C, DMS or C, but not Et 3 ), some of which have been used as auxiliary base in catalytic alcohols dehydrogenation [1]. The mechanism of the H 2 activation and C-H bond formation involves intramolecular cooperation between the structurally remote CH 2 H functionality and the metal center and proceeds without the change of the oxidation state of the metal. This work was financially supported by the Russian Foundation for Basic Research (projects o and ) and by the German-Russian Interdisciplinary Science Center (G- RISC) funded by the German Federal Foreign ffice via the German Academic Exchange Service (DAAD) (projects o. C-2011b-4 and C-2012a-4). 1. S. Musa, I. Shaposhnikov, S. Cohen, D. Gelman, Angew. Chem. Int. Ed. 2011, 50, Musa, S.; Filippov,. A.; Belkova,. V.; Shubina, E. S.; Silantyev, G. A.; Ackermann, L.; Gelman, D. Chem. Eur. J. 2013, 19,

89 C28 RECET DEVELPMET F THE FRAGMET MLECULR RBITAL METHD K. Kitaura Department of Computational Science, Graduate School of System Informatics, Kobe University, Chuo-ku, Kobe, , Japan The fragment molecular orbital (FM) method[1] is an approximate ab initio M computational method for vary large molecules such as proteins. In the method a molecule is divided into fragments and ab initio M calculations are performed on the fragments, their dimers and optionally trimers to obtain the total enegy and other properties of the whole molecule. The method reproduces regular ab initio properties with good accuracy. Various FM-based correlation methods have been developed including density functional theory (DFT), 2 nd order Møller-Plesset perturbation theory (MP2), coupled cluster theory (CC), and MCSCF. Polarisable continuum model (PCM) was interfaced with FM, allowing one to treat solvent effects of real size proteins. The FM codes been incorporated in GAMESS-US[2]. Recently, We have developed the analytical energy gradients [3] and the second derivatives[4] in FM. In this presentation, I will talk about the applications to geometry optimization, MD simulation, and vibrational frequency calculations of large molecular systems. [1] The faragment Molecular rbital Method: Practical Applications to Large Molecular Systems, Dmitri.G..Fedorov, Kazuo Kitaura, Eds., CRC press, Boca Raton, [2] GAMESS, [3] T. agata, et al., J. Chem. Phys. 135, (2011) [4] H. akata, et al., J. Chem. Phys. 138, (2013) 89

90 C29 MDELIG ADSRPTI I ASCALE DEFECTIVE Pd 2 -GRAPHEE SYSTEMS M.V. Polynski, V.P. Ananikov ZIC RAS, Leninsky prospekt, 47, Moscow, Russia; MSU, Faculty of Chemistry, 1-3 Leninskiye Gory, Moscow, GSP-1, Russia Quantum chemical modeling of transition metal particle adsorption on defeted graphene is still challenging due to the fact that periodic systems of tens or even hundreds of atoms have to be considered. We use DFT methods to evaluate Pd 2 affinity to defect sites on graphene surface. GPW method [1] implemented in CP2k program [2] (version 2.6, development) was used for all the computations presented. Spin-polarized computations with dispersion-corrected PBE-D3 functional were performed in all cases unless specified explicitly. GTH-type pseudopotentials for PBE functional and DZVP-MLPT-SR-GTH basis set were used. The model systems were treated as 2D-periodic unless specified explicitly. The geometry optimizations were performed with the BFGS algorithm. Cell parameters were kept fixed during geometry optimizations. Pd 2 molecules were placed near a defect in several spatial configurations and this model systems were subjected to geometry optimization. The affinity of Pd 2 species to various point- and 1Ddefects, and steppings was evaluated, and both magnetic and non-magnetic states were found. The PBE-D3 method allowed to model a system with both covalent and non-covalent interactions. oteworthy, the model systems are truly nanoscale (the cell vectors are longer than ~2 nm) and contain up to ~430 atoms. ptimized structures of Pd 2 binded to double vacancy defect site (left) and Stone-Wales-type defect site (right). The reported study was supported by the Supercomputing Center of Lomonosov Moscow State University [3]. [1] VandeVondele, J.; Krack, M.; Mohamed, F.; Parrinello, M.; Chassaing, T.; Hutter, J. Comp. Phys. Commun. 2005, 167, 103. [2] Hutter, J.; Iannuzzi, M.; Schiffmann, F.; VandeVondele, J. Wiley Interdisciplinary Reviews: Computational Molecular Science 2014, 4, 15. [3] Sadovnichy, V.; Tikhonravov, A.; Voevodin, Vl.; panasenko, V. "Lomonosov": Supercomputing at Moscow State University. In Contemporary High Performance Computing: From Petascale toward Exascale; Vetter, J. S., Ed.; Chapman & Hall/CRC Computational Science, CRC Press: Boca Raton, USA, 2013; pp

91 C30 CLUSTER EFFECT I DECHLRIATI F RGACHLRIDES BY BIMETALLIC Au-Ag SYSTEM: EXPERIMETAL AD THERETICAL STUDY L.V. Romashov, L.L. Khemchyan, E.G. Gordeev, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky prosp. 47, Moscow , Russia Environmental pollution by various chlorinated organic compounds is the problem of great importance nowadays. Various aliphatic and aromatic chlorides have found applications as solvents, dry cleaning fluids, degreasing agents, pesticides, insecticides etc. and have been produced in large quantities during the last decades. Extensive use and chemical stability of chlorinated compounds led to widespread contamination of environment by these pollutants. [1] In recent decades interesting results were achieved using bimetallic systems as promoters of dechlorination process. Interaction between different metal atoms results in superior properties, which significantly exceed a simple combination of individual metals. [2-5] In spite of very promising potential, the origin of bimetallic effect remains unclear and mechanistic picture of bimetallic dechlorination is an open question. Experimental study of dechlorinative activity of Au/Ag bimetallic system has shown formation of a variety of chlorinated bimetallic Au/Ag clusters with well-defined Au:Ag ratio from 1:1 to 4:1 (Figure 1). It is the formation of the Au/Ag cluster species that mediated C-Cl bond breakage, since neither Au nor Ag species alone exhibited a comparable activity (Figure 2). The nature of the products and the mechanism of dechlorination were investigated by ESI-MS, GC-MS, MR and by quantum chemical calculations at the M06/6-311G(d)&SDD level of theory. It was revealed that formation of bimetallic clusters facilitated dechlorination activity due to thermodynamic factor. An appropriate Au:Ag ratio for efficient hydrodechlorination process was determined in a joint experimental and theoretical study carried out in the present work. High activity of the designed bimetallic system made it possible to carry out dechlorination process under mild conditions at room temperature. Figure 1. Example of detected bimetallic Figure 2. Bimetallic effect in dechlorination cluster (optimized geometry). reaction. [1] Thornton, J., Pandora's Poison: Chlorine, Health, and a ew Environmental Strategy. MIT Press: MA, [2] utt, M..; Hughes, J. B.; Wong, M. S. Environ. Sci. Technol. 2005, 39, [3] De Corte, S.; Sabbe, T.; Hennebel, T.; Vanhaecke, L.; De Gusseme, B.; Verstraete, W.; Boon,. Water Res. 2012, 46, [4] De Corte, S.; Hennebel, T.; Fitts, J. P.; Sabbe, T.; Biznuk, V.; Verschuere, S.; van der Lelie, D.; Verstraete, W.; Boon,. Environ. Sci. Technol. 2011, 45, [5] Lambert, S.; Ferauche, F.; Brasseur, A.; Pirard, J. P.; Heinrichs, B. Catal. Today 2005, 100,

92 C31 PRPHYRI-FULLEREE DYADS CVALETLY LIKED VIA PYRRL[3,4-C]PYRRLE LIKER: THE WAY T MLECULES FRMIG LG-LIVED CHARGE-SEPARATED STATE A.S. Konev, P.I. Prolubnikov, A.F. Khlebnikov, A.S. Mereshchenko, A.V. Povolotskiy,.V. Levin St. Petersburg State University, Institute of Chemistry, St. Petersburg, Russian Federation Porphyrinofullerenes represent promising materials for artificial photosynthesis and for construction of organic photovoltaic devices 1 due to their ability to form charge-separated state (CS) upon irradiation with light. The lifetime of the CS thus formed ranges from pico- 2 to microsecond 3 range, depending on the structure of the dyad and on the conditions of irradiation. The larger the lifetime of the CS, the higher is the probability of worthwhile intermolecular electron transfer from a photochemically generated radical-ion pair, making thus a creation of the systems that are capable to form a long-lived CS an important task. Analysis of the relevant literature shows that a porphyrin-fullerene dyad with rigid linker that enables spatial separation of the chromophors and fixes them in face-to-edge orientation, so that their π-systems are virtually orthogonal one to another, should reduce the rate of back-electron transfer and enhance thus the lifetime of the CS. Keeping in mind this strategy of achieving longlived CS species, we synthesized a series of covalently linked porphyrin-fullerene dyads with a rigid pyrrolo[3,4-c]pyrrolic linker that meets the above requirements and studied them by means of transient absorption spectroscopy and cyclic voltammetry. The lifetime of the charge separated state constituted up to 4 μs, depending on the substituents in the porphyrin core. The effect of the porphyrin substituent on the lifetime of the CS was rationalized on the basis of DFT and TD-DFT B3LYP(6-31G(d)) calculations of ground and excited electronic states of model compounds. 532 nm C 2 Et C 2 Et H 2 Et 2 C Et 2 C C 2 Et H 2 C 2 Et H H Ar Ar H Ar-CH Ar F up to 4 μs References 1. D. M. Guldi, Chem. Soc. Rev., 2002, 31, e.g.:.v. Tkachenko, H. Lemmetyinen, J. Sonoda, K. hkubo, T. Sato, H. Imahori, Sh. Fukuzumi, J. Phys. Chem. A, 2003, 107, e.g.: M.E. El-Khouly, K.-J. Han, K.-Y. Kay, Sh. Fukuzumi, Eur. J. Chem. Phys. Phys. Chem., 2010, 11, The work was financially supported by the Russian Foundation for Basic Research (Grant o ), St. Petersburg State University (Grants o , ) and St. Petersburg State University/DAAD joint program (A / ). P 92

93 C32 PALLADIUM-CATALYZED CASCADE AULATI F ALKYES WITH UACTIVATED ALKEES I IIC LIQUIDS J.-X. Li, S.-R. Yang, H.-F. Jiang South China University of Technology, School of Chemistry and Chemical Engineering, Guangzhou, P. R. China Transition metal-catalyzed carbon-carbon or/and carbon-heteroatom bond formations have attracted considerable attention over the past decades, owing to their easy access to highly functionalized molecules in an efficient, atom- and step-economical way. [1] Particularly, palladium-catalyzed cascade reactions have been emerging as a captivating branch of organic chemistry, associating with the mild reaction conditions and excellent functional group tolerance in a fashion of green chemistry. [2] n the other hand, ionic liquids offer an alternative and ecologically sound medium in comparison to conventional organic solvents, as they are nonvolatile, recyclable, highly compatible with transition metal catalysts, limited miscibility with common solvents enables easy product and catalyst separation with the retention of catalyst activity in the ionic phase. [3] Recently, we have investigated various palladium(ii)-catalyzed cascade transformations of alkynes and alkenes in ionic liquids (Scheme 1, Path I-III). As part of our research programs in nucleopalladation and Pd-catalyzed cross-coupling reactions in ionic liquids, we herein present the first example of palladium-catalyzed intermolecular cascade annulation of alkynes with unactivated alkenes in ionic liquids to afford a series of functionalized alkene products (Scheme 1, Path IV). Scheme 1 Reference: [1] Gulevich, A. V.; Dudnik, A. S.; Chernyak,.; Gevorgyan,V. Chem. Rev. 2013, 113, [2] Wu, W.; Jiang, H. Acc. Chem. Res. 2012, 45, [3] Giernoth, R. Angew. Chem., Int. Ed. 2010, 49,

94 C33 SYTHESIS F BEZTHIADIAZLE CMPUDS FR PTICAL MATERIALS Y.L. Li, S.H. Chen Institute of Chemistry, Chinese Academy of Sciences,CAS Key Laboratory of rganic Solids, Beijing, P.R. China The nature of the substituent groups greatly influences the structural and photophysical properties of D/A molecules. The nature of the linkage between the D and A units also influences the structures and photophysical properties of intramolecular charge transfer (ICT) compounds. 1 For example, in the D/A molecules BSC and BEC containing carbazole moieties as their D moieties and a 2 -substituted benzothiadiazole as their A moiety, X-ray crystal data elucidated multiple intermolecular interactions in these systems. 2 These interactions were the main driving forces directing the self-organization of the microstructures, with the different linkages exhibiting distinctly different self-assembly behavior. Most D/A-substituted compounds suffer from aggregation-caused emission quenching (ACQ) in the solid phase, greatly limiting their applications. 3 We have observed aggregation-induced emission (AIE) effects for several of our ICT compounds, including the carbazole- and benzothiadiazole-based BSE, BEC, BT-6 and BT-7. These prepared nanostructures exhibit green, yellow, and especially red emissions. In addition, the distance-dependent photoluminescence image of a single microrod of BT-7 measured using a near-field scanning optical microscope indicated that these microrods possess outstanding optical waveguide properties, with a waveguide efficiency (a) of db μm 1 and no obvious red-shift. 4 References 1. Liu, H.; Xu, J.; Li, Y.; Li, Y. Acc. Chem. Res. 2010, 43(12), Chen, S.; Qin, Z.; Liu, T.; Wu, X.; Li, Y.; Liu, H.; Song, Y.; Li, Y. Phys. Chem. Chem. Phys., 2013, 15, Xu, J.; Zheng, H.; Liu, H.; Zhou, C.; Zhao, Y.; Li, Y.; Li, Y. J. Phys. Chem. C 2010, 114, Chen, S.; Chen,.; Yan, Y.; Liu, T.; Yu, Y.; Li, Y.; Liu, H.; Zhao, Y.; Li, Y. Chem. Commun., 2012, 48,

95 C34 DEDRIMERS AD BIMASS: SYTHESIS, CATALYSIS AD ECAPSULATI S. Bouquillon, B. Menot, J. Stopinski ICMR, Universitй Reims Champagne Ardenne For several years, our research team is interested in the development of new families of dendrimers using organic by-products from biomass (pentoses, glycerin or corresponding by-products). Some glyco-or glycerodendrimers derived from PPI (polypropylene imines) were already obtained, and valued in the domains of aqueous catalysis and encapsulation of metallic salts or emergent pollutants [1,2]. Glycodendrimers were also previously synthetized and used for the preparation and the stabilization of metallic nanoparticles (Pt, Pd, Au), which could be used in aqueous catalysis [3]. The objective of this presentation is, at first, to describe the synthesis of nitrogenous glycerodendrimers derived of polypropyleneimines (PPis) or of polyamidoamines (PAMAMs) and, secondly, to demonstrate their potential in catalyses of hydrogenation and oxidation in the water and in encapsulation of organic pollutants (Figure 1). Figure 1: Catalysis and encapsulation in biomass derived dendrimers [1] C. Hadad, J-P Majoral, J. Muzart, A-M Caminade, S. Bouquillon, Tetrahedron Lett. 2009, 50, [2] S. Balieu, A. El Zein, R. De Sousa, F. Jérôme, A. Tatibouët, S. Gatard, Y. Pouilloux, J. Barrault, P. Rollin, S. Bouquillon, Adv. Synth. & Catal. 2010, 352, [3] a) S. Gatard, L. Liang, L. Salmon, J. Ruiz, D. Astruc, S. Bouquillon, Tetrahedron Lett. 2011, 52, b) S. Gatard, L. Salmon, C. Deraedt, J. Ruiz, D. Astruc, S. Bouquillon Eur. J. Inorg. Chem. 2014,

96 C35 BIISPIRED CHIRAL IIC LIQUIDS AS IVATIVE RGACATALYSTS L.C. Branco REQUIMTE, Departamento de Quнmica, Faculdade de Ciкncias e Tecnologia, Universidade ova de Lisboa, Caparica, Portugal Chiral Ionic Liquids (CILs) can be useful as chiral solvents or chiral selector in some cases [1]. Recent examples showed the possibility to use chiral ILs as efficient organocatalysts or chiral ligands for Asymmetric Aldol and Michael additions as well as Sharpless dihydroxylation of olefins, among others [2,3]. Asymmetric organocatalysis is an intensively developing area of current organic chemistry in recent years [4]. Aldol and Michael reactions play an important role in carbon-carbon bond forming reaction. The interest of chiral molecules as novel catalysts remains to grow as a wide range of small organic molecules, including L-aminoacids moieties such as L- proline and L-cysteine, which showed to be efficient organocatalysis for asymmetric reactions [5]. In this context, we have been developed novel Bioinspired chiral ionic liquids based on L-cysteine and L-proline derivatives as well as task-specific nucleotides in order to test as chiral organocatalyst of asymmetric organocatalysis and metal catalysis. direct aldol reactions between ketones with nitrobenzaldehydes. For some cases, it was possible to obtain the pure chiral products in good yields and enantiomeric excesses comparable with the conventional systems. Asymmetric direct aldol reactions, Michael additions, Suzuki and Mannich reactions using some bioinspired CILs as chiral catalyst were also tested. Catalytic recycling processes have been performed using efficient sustainable methodologies. Bioinspired Chiral Ionic Liquid Chiral Recognition Asymmetric catalysis Acknowledgements: This work has been supported by FCT/MCTES (PEst-C/EQB/LA0006/2011, PTDC/CTM/103664/2008 and PTDC/CTM-A/120658/2010 projects) References: [1] J. Ding, D. W. Armstrong, Chirality 2005, 17, 281. [2] a ) A. Lu, T. Liu, R. Wu, Y. Wang, G. Wu, Z. Zhou, J. Fang, C. Tang, J. rg. Chem. 2011, 76, b) L. C. Branco, P. M. P. Gois,. M. T. Lourenco, V. B. Kurteva, C. A. M. Afonso, Chem Comm. 2006, [3] a) L. C. Branco, A. Serbanovic, M.. Ponte, C. A. M. Afonso, ACS Catal. 2011, 1, b). C. A. M Afonso, L. C. Branco,. R. Candeias, P.M.P. Gois,. M. T. Lourenço,. M. M. Mateus, J.. Rosa, Chem. Commun. 2007, [4] K. Bica, P. Gaertner, Eur. J. rg. Chem. 2008, [5] B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc. 2000, 122,

97 C36 THE CMPARIS F CMPUTATIAL METHDS FR THE STUDY F PYRASIDE-IT-FURASIDE REARRAGEMET A.G. Gerbst, V.B. Krylov, D.A. Argunov,.E. ifantiev.d. Zelinsky Institute of rganic Chemistry RAS, Laboratory of Glycoconjugate Chemistry, Moscow, Russia Furanoside units are often encountered in biologically important complex polysaccharides and smaller oligosaccharides. n the other hand, synthetic methods of furanoside modification are less developed than those for pyranosides. Thus a promising strategy for the introduction of a furanoside moiety into a complex saccharide might be to synthesize first the corresponding pyranoside and then convert it into the pyranoside. Recently, in our laboratory we have discovered a novel rearrangement that allows such transformation of a pyranoside into furanoside (PIF) with good yields. This reaction proceeds under per-sulfation conditions in the acid media. In this communication we present the comparison of different quantum chemical methods for the computational study of the PIF mechanism (Fig. 1). It includes the energy calculations of starting molecules and supposed transition states (TS) and intermediates. btained data are correlated with the observed reaction kinetics. TS1 - TS2-3 S post-reaction complex HH 2 C HH 2 C H 3 S - S Figure 1. Proposed mechanism of the PIF transformation. Ab initio calculations were used in this work with different split-valence basis sets. Taking 6-31G type basis sets we varied number of diffuse and polarization functions in order to find the optimal basis set, which would allow fast calculation with reasonable accuracy. Finally basis set 6-31+G*, having one diffuse and one polarization function was found to give most satisfactory results. Acknowledgement. This work was supported by the grant from Division of Chemistry and Material Sciences of Russian Academy of Sciences, Program 1. 97

98 C37 GLD(I) CATALYSED ASYMMETRIC HYDRAMIATI F ALKEES I MILD CDITIS F. Agbossou-iedercorn 1, M.A. Abadie 1, F. Medina 1, X. Trivelli 2, F. Capet 1, C. Michon University Lille ord de France, UCCS UMR 8181 CRS, ESCL C7 CS90108, Villeneuve d Ascq Cedex, France 2 - University Lille ord de France, LGSF UMR 8576, USTL Villeneuve d Ascq Cedex, France Gold catalysed hydroamination reactions were recently highlighted on alkenes, 1a,b allenes 1c and dienes 1a,d substrates for both intra- and intermolecular reactions. However, achieving highly selective gold catalysed hydroamination of alkenes, activated or not, remains a challenging endeavor and we would like to report herein our last results. 2 First, following our researches on activated alkenes 2a,b and allenes, 2c the intramolecular gold(i) catalysed asymmetric hydroamination of alkenes was studied screening a wide range of monophosphines. Specially designed phosphoramidite ligands proved to lead to active mononuclear gold(i) catalysts when combined with silver salts. Indeed, chiral amines were obtained in high yields and average enantioselectivities using mild reaction conditions (Scheme 1). 2d Second, various binuclear gold(i) catalysts based on selected diphosphine ligands were studied. When combined with a silver salt, a specific gold(i) species proved to perform efficiently the intramolecular hydroamination of alkenes at mild temperatures with high yields and enantioselectivities (Scheme 1). 2e The molecular structure of catalyst was determined by X-Ray diffraction analyses and DSY MR experiments in order to check the influence of silver salts and water. 3 Indeed, water proved to enhance significantly reaction yields and enantioselectivities. Scheme 1. 1 (a) X. Giner, C. ájera, G.Kovács, A. Lledós, G. Ujaque, Adv. Synth. Catal. 2011, 353, 3451; (b) M. Kojima, K. Mikami, Synlett 2012, 23, 57; (c) K. L. Butler, M. Tragni, R. A. Widenhoefer, Angew. Chem. Int. Ed. 2012, 51, 5175; (d). Kanno, W. Kuriyama, J. Z. Wang, D. F. Toste, Angew. Chem. Int. Ed. 2011, 50, 9919; 2 (a) F. Medina, C. Michon, F. Agbossou-iedercorn, Eur. J. rg. Chem. 2012, 6218; (b) F. Medina et al., Comptes Rendus Chimie 2013, 16, 311; (c) C. Michon, F. Medina, M.-A. Abadie, F. Agbossou- iedercorn rganometallics 2013, 32, 5589; (d) C. Michon, M.-A. Abadie, F. Medina, F. Agbossou- iedercorn Catalysis Today 2014, doi /j.cattod ; (e) M.-A. Abadie, X. Trivelli, F. Medina, F. Capet, F. Agbossou-iedercorn, C. Michon, submitted. 3 (a) A. Homs, I. Escofet, A. M. Echavarren, rg. Lett. 2013, 15, 5782; (b) Y. Tang, B. Yu, RSC Adv. 2012, 2, 12686; (c) D. Wang, R. Cai, S. Sharma, J. Jirak, S. K. Thummanapelli,. G. Akhmedov, H. Zhang, X. Liu, J. L. Petersen, X. Shi, J. Am. Chem. Soc. 2012, 134,

99 C38 SUPRAMLECULAR GELS FR CATALYTIC TRASFRMATIS AD A-MATERIALS SYTHESIS S. Vatsadze, V. uriev, A. Medved ko Chemistry Department, Lomonosov Moscow State University Supramolecular gels are gels formed by immobilizations of liquid phase on the 3D network of entangled nano-fibres which themselves are the result of supramolecular polymerization and selforganization [1]. In this report we will focus on the following: 1. supramolecular gels belongs to the family of «smart materials» since they could change their structures in response to the external stimuli; 2. the control over structural and practical properties of gels could be engineered at the stage of molecule design; 3. the possibility of using the organogel as a template for the synthesis of the inorganic replica; 4. post-synthetic transformations, i.e. supercritical fluid drying, expands the scope of materials properties; 5. metal-containing supramolecular gels combine the properties of both heterogeneous and homogeneous catalysts. We thank financial support by RFBR (grant # ). 1. V.P.Ananikov, L.L.Khemchyan, Yu.V.Ivanova, V.I.Bukhtiyarov, A.M.Sorokin, I.P.Prosvirin, S.Z.Vatsadze, A.V.Medved'ko, V..uriev, A.D.Dilman, V.V.Levin, I.V.Koptyug, K.V.Kovtunov, V.V.Zhivonitko, V.A.Likholobov, A.V.Romanenko, P.A.Simonov, V.G.enajdenko,.I.Shmatova, V.M.Muzalevskiy, M.S.echaev, A.F.Asachenko,.S.Morozov, P.B.Dzhevakov, S..sipov, D.V.Vorobyeva, M.A.Topchiy, M.A.Zotova, S.A.Ponomarenko,.V.Borshchev, Y..Luponosov, A.A.Rempel, A.A.Valeeva, A.Yu.Stakheev,.V.Turova, I.S.Mashkovsky, S.V.Sysolyatin, V.V.Malykhin, G.A.Bukhtiyarova, A..Terent'ev, I.B.Krylov. "Development of new methods in modern selective organic synthesis: preparation of functionalized molecules with atomic precision", Russ.Chem.Rev., 2014, 83 (10), in press. DI: /RC2014v083n10ABEH

100 C39 SYTHESIS AD TRASFRMATIS F STRAIED PLYITRGE CMPUDS M.A. Kuznetsov, A.S. Pankova Saint Petersburg State University, Institute of Chemistry, Saint Petersburg, Russia The oxidation of many -aminoheterocycles in the presence of unsaturated compounds is a general way to -aminoaziridine derivatives containing a strained three-membered ring and combining two heterocyclic moieties in one molecule via a weak - bond. This reaction, the so-called oxidative aminoaziridination, is applicable to a wide range of unsaturated substrates and proceeds in a stereospecific manner with a complete retention of a spatial arrangement of substituents at >C=C< bond in the resulted -aminoaziridines. In this way we have synthesized a set of alkynylaziridines, which possess three endothermic fragments in one molecule, and large series of adducts to styrenes, unsaturated carbonyl compounds, a lot of spiroaziridines etc. With alkenylpyrazoles the expected heterocyclic chains are usually formed in good yields. And it was the same for alkenyl-1,2,4- and 1,3,4-oxadiazoles with one or two double bonds in the side chains. The reaction with alkenylfuranes leads to the unsaturated acyclic compounds exclusively, and can be used for a stereospecific synthesis of 4-oxohexa-2,5-dienal derivatives with (Z)-configuration of 2,3-C=C bond. The oxidative aminoaziridination of the very similar alkenylthiophenes leads to expected adducts onto exocyclic C=C bond, but with thiophene itself and even with selenophene gave the very interesting tricyclic diadducts, though in low yields. Since the classical works of R. Huisgen in 60-ies it is well known that the C-C bond in aziridines can be broken thermally or upon irradiation giving the octet-stabilized 1,3-dipoles, so-called azomethyne ylides, which can be involved in 1,3-dipolar cycloaddition reactions. We have found that for cis- and trans-2,3-disubstituted 1-phthalimidoaziridines this set of transformations proceeds in a stereospecific manner as a concerted process which obeys the rules of orbital symmetry conservation. The intramolecular cycloaddition of 1,3-dipoles should lead to the polycyclic condensed compounds, which are of interest in many aspects. And we have realized it for some - phthalimidoaziridines with sterically accessible, but inactivated C=C and C C bonds. In some cases the regioisomeric imines appeared as the main components of these reaction mixtures. This result caused by 1,2-migration of phthalimidyl rest in the intermediate ylides is often the general one for arylsubstituted aziridines. n another hand, an attempt for intramolecular cycloaddition of aziridines with carbonyl substituents led to quite another products: the 1,5- electrocyclization of an intermediate ylide with a participation of C= bond followed by loss of phthalimide fragment provided aromatic oxazoles in good yields. This transformation of carbonylsubstituted azomethyne ylides into oxazoles competes with an intermolecular cycloaddition too. The yields of oxazoles in all these reactions usually vary from good up to excellent. Taking it into account we have offered the simple and efficient transformation of α,β-unsaturated carbonyl compounds into the corresponding oxazoles via -phthalimidoaziridines or even via -arylsulfonylaziridines. This approach is applicable to the synthesis of oxazoles with ethynyl substituent as well. In the case of C-alkenylaziridines, the intermediate ylide contains a conjugated C=C bond, and another kind of 1,5-electrocyclization into pyrrolines is conceivable. Combination of the strained three-membered rings and hydrazine moiety makes cyclopropylhydrazines highly energetic compounds. Beside it, the hydrazine fragment occurs in a variety of bioactive compounds. But only two mono- and 1,2-dicyclopropylhydrazine out of five possible cyclopropylhydrazines have been known till now. And the last part of our work is devoted to the synthesis of still unknown cyclopropylsubstituted hydrazines. This work was supported by Russian Scientific Fond (research grant no ). 100

101 C40 EW TYPE F REACTIVITY F DR-ACCEPTR CYCLPRPAES: GaCl 3 -MEDIATED GEERATI F FRMAL 1,2- AD 1,4-DIPLES R.A. ovikov, A.V. Tarasova, Y.V. Tomilov. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow, Russian Federation A new type of reactivity of donor-acceptor cyclopropanes has been discovered. n treatment with anhydrous GaCl 3, they react as sources of even-numbered 1,2- and 1,4-dipoles instead of the classical odd-numbered 1,3-dipoles due to migration of positive charge from the benzyl center. This type of reactivity has been demonstrated for new reactions, viz., cyclodimerizations of donoracceptor cyclopropanes that occur as [2+2]-, [3+2]-, [4+2]-, [5+2]-, [4+3]-, and [5+4]-annulation. The [4+2]-annulation of 2-arylcyclopropane-1,1-dicarboxylates to give polysubstituted 2- aryltetralins has been developed in a preparative version that provides exceedingly high regio- and diastereoselectivity and high yields. The strategy for selective cross-combination of donor-acceptor cyclopropanes was also been developed. The mechanisms of the discovered reactions involving the formation of a comparatively stable 1,2-ylide intermediate have been studied. Hitherto unknown complexes of donor-acceptor cyclopropanes with GaCl 3 belonging to a new type and having a 1,2- dipole (ylide) structure have been obtained and characterized by 1D, 2D and DSY MR spectroscopy. Futher transformations of this complex have also been demonstrated. ew 1,2 - and 1,4 -D ipolar S ynthetic E quiva lents C 2 M e G a C l 3 A r C 2 M e M e 2 C C 2 M e M e 2 C M e 2 C A r C 2 M e C 2 M e C lassical 1,3 -D ipole R A r [4 + 2 ] [2 + 2 ] R 4 R 5 C 2 M e C 2 M e M e 2 C M e 2 C C 2 M e C 2 M e R 3 R 1 A r R 2 A r The discovered [4+2]-annulation of DAC is a synthetically valuable process that allows the onestage assembly of polysubstituted tetralins with exceptionally high regio- and diastereoselectivity. The latter may be of interest as synthons in organic synthesis and as compounds possessing biological activity. In fact, the aryltetralin moiety occurs in the structures of a number of compounds that have been isolated from various natural sources and manifest a broad spectrum of biological activity, including antitumor activity. This work was supported by the Russian Federation President Council for Grants (Program for State Support of Leading Scientific Schools of the Russian Federation, grant no. Sh ) Selected Publications: Tetrahedron Lett., 2011, 52, ; rganometallics, 2012, 31, ; J. rg. Chem., 2012, 77, ; rg. Lett., 2013, 15, ; Helv. Chim. Acta., 2013, 96, ; Angew. Chem. Int. Ed., 2014, 53,

102 C41 EW REACTIS F TATALUM(V) AMIDES M.. Sokolov, A.L. Gushchin, A.V. Rogachev, P.A. Abramov ikolaev Institute of Inorganic Chemistry Transition metal amides are highly reactive compounds which are much employed as reagents, ligand transfer agents, or precursors for more complex molecules. The ready cleavage of the highly polar M-R 2 bond makes the amides particularly important synthons for a wide range of new compounds and materials. The M-R 2 bond can be easily cleaved by protonation using various reagents with acidic E-H bonds (alcohols, thiols, secondary phosphines, pyrazoles etc.). Reactive small molecules such as CS 2 or C 2 undergo insertion with the formation of dithiocarbamates and carbamates. In this work we report synthesis of new Ta coordination compounds and clusters by reactions of Ta(Me 2 ) 5 with CS 2, Ph 2 PH and pyrazol; with or without subsequent treatment with sulfur. Ta(Me 2 ) 5 easily react with CS 2 with the formation of [Ta(S 2 CMe 2 ) 3 ( -CH 2 -Me)] (1). The formation of 1 can be explained as triple insertion of CS 2 followed by α-elimination of a HMe 2 molecule. Excess of CS 2 leads to the formation (in CH 2 Cl 2 ) of [Ta(S 2 CMe 2 ) 4 ]Cl (2). Cyclic voltammetry shows that [Ta(S 2 CMe 2 ) 4 ] + can be reversibly reduced to the neutral [Ta(S 2 CMe 2 ) 4 ], the Ta(V)/Ta(IV) couple having E 1/ V vs. Ag/AgCl. Reaction with CS 2 in the presence of S 8 leads to a complex mixture of Ta(V) dithiocarbamates [TaS(S 2 CMe 2 ) 3 ] (3), [Ta(S 2 )(S 2 CMe 2 ) 3 ] (4), and a perthiocarbamate complex [TaS(S 3 CMe 2 )(S 2 CMe 2 ) 2 ] (5). HPPh 2 rapidly reacts with Ta(Me 2 ) 5 with the formation of an unstable product, which after treatment with S 8 yields green crystals of a cuboidal cluster, [Ta 4 S 4 (μ-s 2 PPh 2 ) 4 (S 2 PPh 2 ) 2 ] (6), which is, to the best of our knowledge, the first cluster with the {Ta 4 S 4 } core. Long Ta-Ta distances ( Å) correspond to electron-deficient (only six of the required 12 e) M-M bonding in the cluster core. 3,5-dimethylpyrazol (PzH) is a stronger -H acid than Me 2 H, and reacts with Ta(Me 2 ) 5 with the formation of yellow crystals of the pentakis(pyrazolate), [Ta(pz) 5 ] (7). According to X-ray data, the Ta atom achieves C 8 by coordinating three pz ligands in the 2 1, and two pz ligands in the mode. All the compounds have been characterized by single crystal X-ray analysis. Reactivity of complexes 1-7 is being investigated. The work was supported by RFBR grant o [1] M.F. Lappert, A. Protchenko, P. Power, A. Seeber. Metal-Amide chemistry, 2009, John Wiley and Sons, 355 pp. 102

103 C42 STRUCTURE-REACTIVITY RELATISHIPS I THE REACTIS F C- AMI-1H-1,2,4-TRIAZLES WITH ELECTRPHILES V.M. Chernyshev, D.A. Pyatakov, A.V. Astakhov, A.I. Evdokimova, A.Yu. Chernenko Platov South-Russian State Polytechnic University (PI), ovocherkassk, Russia Molecules of C-amino-1,2,4-triazoles (AT) contain several alternative nucleophilic centers, namely H 2 group and any of the ring nitrogen atoms, and therefore can be considered as multifunctional nucleophilic reagents. Such multifunctionality, on the one hand, opens up exciting possibilities for the synthesis of various substituted triazoles and condensed heterocycles [1], however, on the other hand, it causes the problem of selectivity [2, 3]. The present report discusses relationships between the structure of AT and their reactivity towards electrophiles and some novel approaches to the control of selectivity. n the basis of computational and experimental methods it was established that the position of the endocyclic substituent R has a significant influence on the reactivity of C-amino-1-R-1,2,4- triazoles. The global nucleophilicity of the 1-substituted 3-amino-1,2,4-triazoles is higher than the 1-substituted 5-amino-1,2,4-triazoles. Therewith, amino group in the position 3 of triazole ring is substantially more nucleophilic than in the position 5. The atoms -2 and -4 of triazole ring as well as the 3-H 2 group are the most favorable sites in the 1-substituted C-amino-1,2,4-triazoles for the attack of electrophiles. Some new approaches to the selective synthesis of substituted triazoles and condensed heterocycles via reactions of AT with electrophilic and bielectrophilic reagents are considered. The structural features and reactions of condensed derivatives of 1,2,4-triazole including some new recyclizations are discussed. Acknowledgements This work was financially supported by the Russian Foundation for Basic Research (grant no ) and in part by the Ministry of Education and Science of the Russian Federation, State contract o. 2014/143 (project o. 2945). References [1] Curtis, A.D.M.; Jennings,. 1,2,4-Triazoles. In Comprehensive Heterocyclic Chemistry III. Elsevier: xford, V. 5. P [2] Chernyshev, V.M.; Astakhov, A.V.; Starikova, Z.A. Tetrahedron 2010, 66, [3] Chernyshev, V.M.; Pyatakov, D.A.; Sokolov, A..; Astakhov, A.V.; Gladkov, E.S.; Shishkina, S.V.; Shishkin,.V. Tetrahedron. 2014, 70,

104 C43 SILYL ITRATES I THE VEL [3+3]-CYCLADDITI REACTI WITH DR-ACCEPTR CYCLPRPAES A.A. Mikhaylov 1, R.A. ovikov 1, D.E. Arkhipov 2, S.L. Ioffe D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation 2 - A.. esmeyanov Institute of rganoelement Compounds, Russian Academy of Sciences, Moscow, Russian Federation Cycloaddition reactions are one of the most effective tools for rapid generation of molecular complexity. 1 Recently, the formal cycloadditions have evoked special attention due to the intriguing ability of donor-acceptor cyclopropanes, mainly 1,1-cyclopropane diesters 1, to behave as equivalents of 1,3-zwitterions under Lewis acid catalysis. 2,3 The formal [3+3]-cycloaddition, discovered by Kerr and co-workers on the nitrones in 2003, 4 has already proved itself as a powerful method for six-membered cycles construction. 3 In this respect, silyl nitronates 2 can be considered as perspective substrates for formal cycloaddition chemistry due to their 1,3-dipolaric nature. We have shown that different silyl nitronates 2 derived from both primary and secondary nitro compounds can react with 1,1- cyclopropane diesters 1 giving rise to polysubstituted six-membered nitroso acetals 3. 5 The latters in hand can be easily transformed into isomeric pyrroline--oxides 4 and 5 via novel acid-catalyzed ring contraction/silanol elimination reaction. In the presentation the major regularities of the observed [3+3]-cycloaddition reaction will be discussed. The special attention will be focused on the reasons determining stereochemical outcome of nitroso acetals 3. The work was supported by Russian Foundation for Basic Research (Grants # , ). References 1. M. Juhl, D. Tanner, Chem. Soc. Rev. 2009, 38, C. A. Carson, M. A. Kerr, Chem. Soc. Rev. 2009, 38, T. F. Schneider, J. Kaschel, D. B. Werz, Angew. Chem. Int. Ed. 2014, 53, I. S. Young, M. A. Kerr, Angew. Chem. Int. Ed. 2003, 42, A. A. Mikhaylov, R. A. ovikov, Yu. A. Khomutova, D. E. Arkhipov, A. A. Korlyukov, A. A. Tabolin, Yu. V. Tomilov, S. L. Ioffe, Synlett, submitted. 104

105 C44 SLID-PHASE SYTHESIS F PICER CMPLEXES: EMERGIG ALTERATIVE T CVETIAL SYTHESIS I SLUTI D.V. Aleksanyan, V.A. Kozlov A.. esmeyanov Institute of rganoelement Compounds, Russian Academy of Sciences Pincer complexes featuring a tridentate monoanionic framework have become a privileged class of organometallic compounds, finding extensive application in catalysis, materials science, biochemistry and so on. 1,2 Several synthetic routes, including direct cyclometalation, oxidative addition, and trans(cyclo)metalation, give access to pincer complexes with almost any type of ligands and metal ions, however, the simplest route seems to be direct cyclometalation. umerous examples of direct cyclometalation of pincer ligands have been described in solution, but the literature data on the solid-state synthesis of metallacycles are restricted only to several reports dealing with the thermally induced intramolecular cyclometalation of well-defined coordination complexes leading to monometallacyclic species. Recently we have shown that cyclometalation of pincer ligands can be readily carried out in the solid state simply by heating homogeneous mixtures of a ligand and metal precursor obtained by manual grinding in a mortar. 3 This novel solid-phase approach has now been extended to a range of pincer-type ligands which require the activation of the C H, H, and H bonds and have different ancillary S-, P-, and -donor groups (for selected examples see figure). The results obtained show great potential of the solid-phase cyclometalation as an alternative to the conventional synthesis of complex organometallic compounds in solution. Some aspects of the solid-phase cyclometalation will be discussed based on the results of spectral and thermochemical analyses. Ph Ph P S Pd S Cl Ph Ph P S Pd Cl 105 H Ph 2P Pd Ph Ph S Cl P S Cl Pd Me Ph Ph S P S Pd Cl S P Ph Ph This work was supported by the Russian Foundation for Basic Research (project no mol-a) and the Grant of the President of the Russian Federation for young scientists (project no. MK ). 1. The Chemistry of Pincer Compounds, D. Morales-Morales and C. M. Jensen (Eds.), Elsevier, ew York, rganometallic Pincer Chemistry, G. van Koten and D. Milstein (Eds.), Topics rganomet. Chem., 2013, V. A. Kozlov, D. V. Aleksanyan, M. V. Korobov,. A. Avramenko, R. R. Aysin,. A. Maloshitskaya, A. S. Korlyukov and I. L. dinets, Dalton Trans., 2011, 40, S

106 C45 SYTHETIC APPRACHES AD ELECTRIC PRPERTIES F FUCTIALIZED FULLEREES AS ASIZED PTICAL MLECULAR SWITCHES L.M. Khalilov, A.R. Tuktarov, A.R. Akhmetov, A.A. Khuzin, Z.R. Shakirova, A.R. Tulyabaev, I.I. Kiryanov, V.M. Yanybin, U.M. Dzhemilev Institute of Petrochemistry and Catalysis of RAS At present, the abilities of the manufacturing technology of traditional materials for modern computers have almost peaked. The main factor that restrains creation of modern supercomputers is a critical size of silicon transistors to be reached which are responsible for a quick response. ne possible way to solve the problem is to replace conventional silicon transistors by molecular switches that can be by several orders less than the known smallest devices. Given that the molecular switches must have π-donor groups along with π-acceptor one, we have put forward the idea to use fullerene derivatives, a new allotropic carbon form, that possess high donor-acceptor features. Thus, a new effective methods of synthesis of potential molecular switches and three-dimensional memory elements based on C 60 and C 70 fullerene derivatives have been suggested. Highly selective methods of cycloaddition of organic azides to fullerenes under metalcomplex catalysts have been developed. This gives the individual aziridine- and azahomofullerenes that able to isomerize into each other under influence of UV irradiation. Algorithms of dichotomous features which are responsible for photochromic properties of molecular switches and generating of the new structures with incorporated fullerenes as doping agents directly into the fullerene core and in the attached moieties to activate the donor-acceptor properties and stability of molecular electronic systems. The results of molecular design of new types of optical molecular switches will be done using calculations of the electronic structure and physicochemical properties of fullerene derivatives with modern high-level quantum chemistry approaches (DFT and ab initio) will be discussed. 106

107 C46 CRDIATI CHEMISTRY F BIS(PYRAZLYL)PYRIDIES WITH 3d-TRASITI METALS: RECET DEVELPMET AD PRGRESS.M. Kurnosov Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia Coordination compounds of transition elements with -donor ligands are widely used as catalysts, molecular switches (SC), dye-synthesized solar cell (DSSC). As analogs of terpyridine 2,6-bis(pyrazolyl)pyridines are widely investigated and there are known a lot of results in coordination chemistry of them [1]. Most of results are related to iron complexes and investigation of spin-crossover. The aim of this work is the synthesis and study of complexes of 3d-transition elements with 2,6- bis(pyrazolyl)pyridines. A large library of such ligands has been synthesized. There are two major branches of research copper complexes and iron binuclear complexes with 3,6-bis(pyrazolyl)-1,2,4,5-tetrazine as bridging ligand. It is common fact that such iron complexes can exhibit two-step spin-crossover transition from e.g. HS-HS state to the LS-LS state and also mix-valent species can be stabilized. Also for copper biand polynuclear complexes are much interesting due to the possibility of metal-metal interaction. The resulted complexes were investigated by ESR spectroscopy, electron spectroscopy, mass spectrometry, Fig. 1. Structures of [Cu(Cl)(bPzPy)] 2 (Cl 4 ) 2 (left) and [Cu(Cl)(bPzPy)(Cl 4 )] (right). Fig. 2. The 1D-chains for complex [Cu(bPzPy)(H 2 )( 3 ) 2 ], hydroden bonds are maked by dotted lines. View along the b axis. infrared and Raman spectroscopy, their magnetic properties were measured and calculated by quantumchemical qualculations. For some complexes crystals suitable for X-ray structure analysis were obtained. In the case of iron and cobalt complexes of 2,6-bis(pyrazolyl)pyridines have a monomeric structure regardless of counterions and the introduction of additional ligands capable of acting as bridging ligands halide- and azide- anions. Dimeric complexes with bridging ligands could be obtained for copper and nickel. There is a weak ferromagnetic interaction for dimeric copper complexes with the structure [Cu(Cl)(bPzPy)] 2 (Cl 4 ) 2 (Fig 1.), calculated coupling constant for which is in agreement with the experimental data. For nonsubstituted pyrazole one-dimensional chain with perchlorate-bridging was obtained in the first time (Fig 1.). In some cases 1D-chains or more complicated frameworks are formed by hydrogen bonding (Fig 2.) [2]. Dinuclear iron complexes has been obtain with 3,6-bis(pyrazolyl)-1,2,4,5-tetrazine as bridging ligand and 2,6-bis(pyrazolyl)pyridines the simple ligands. The ground state and possibility of stable mix-valent state depend on the structure of 2,6-bis(pyrazolyl)pyridines. The author thanks Prof. S.I. Troyanov, Prof. Yu.M. Kiselev, Cand.Sc. V.D. Dolzhenko, V.V. Korolev and his students A.A. Vuhovskiy, T.D. Ksenofontova and A.G. Gevondyan. 1. M.A. Halcrow, Coord. Chem. Rev. 2005, 249, Dolzhenko, V. D., Kurnosov,. M. and Troyanov, S. I. (2014), Z. anorg. allg. Chem., 640:

108 C47 PLYMER-STABILIZED PALLADIUM APARTICLES AS EFFECTIVE CATALYSTS F SELECTIVE HYDRGEATI F ALKILS L.Zh. ikoshvili 1, V.G. Matveeva 1, E.M. Sulman 1, B.D. Stein 2, L.M. Bronstein Tver Technical University, , Tver, Russia 2 - Indiana University, Department of Biology, I 47405, Bloomington, USA 3 - Indiana University, Department of Chemistry, I 47405, Bloomington, USA; King Abdulaziz University, Jeddah 21589, Saudi Arabia Selective hydrogenation of unsaturated carbon-carbon bond using Pd nanoparticles (Ps) is of great importance as widely applicable in synthesis of fine chemicals, vitamins and pharmaceuticals. ne of the most complicated problems along with achieving of high activity, selectivity and stability of catalytic system is control over the Pd P size, size distribution and morphology [1, 2]. To achieve appropriate selectivity, traditional industrial catalysts of alkyne hydrogenation require the addition of modifiers, which are not desirable for environment [3-5]. Though, in the case of terminal alkynes, neither the control of P morphology [2] nor modification [4] yield the benefits, P size and stabilizing environment play crucial role and the selectivity problem still exists [5]. Among the organic porous supports for catalyst synthesis, hypercrosslinked polystyrene (HPS) received increased attention due to its high crosslinking degree, which can be higher than 100%. The unique property of HPS is the ability to swell in different solvents, which favors inclusion of various organometallic compounds in the HPS matrix. Besides, HPS based catalysts allow control of the P formation due to a cage effect (by limiting the P size with the pore size) along with controlling the precursors and reduction conditions. In this work the incorporation of Pd Ps in polymeric matrix of HPS at variation of metal loading, precursor nature and type of polymer (influence of fictionalization) is discussed. Series of Pd/HPS catalysts was tested in the reaction of selective hydrogenation of 2-methyl-3-butyne-2-ol, which is intermediate of synthesis of fragrant substances and vitamins (E and K) and model compound of industrially important acetylene alcohols C 10 and C 15. Physicochemical characterization was performed via XPS, liquid nitrogen physisorption and TEM. Developed catalysts were found to contain Pd Ps with mean diameter of 3-5 nm (Fig. 1) and provide high selectivity (up to 98.5% at 100% of the substrate conversion). Besides, synthesized HPS-based nanocomposites were highly active in comparison with traditional hydrogenation catalyst (i.e. 2%(wt.)-Pd/CaC 3 ), and no leaching of catalytically active compound was observed. Financial support was provided by Seventh Framework Programme of the European Community (CP-IP PLYCAT) and Ministry of education and science of Russia (contract P1345). References 1.. Semagina, L. Kiwi-Minsker. Catal. Lett. 127 (2009) L. Kiwi-Minsker, M. Crespo-Quesada. Top. Catal. 55 (2012) P.W. Albers, K. Möbus, Ch.D. Frost, S.F. Parker. J. Phys. Chem. C. 115 (2011) J.A. Anderson, J. Mellor, R.P.K. Wells. J. Catal. 261 (2009) P.T. Witte, P.H. Berben, S. Boland, E.H. Boymans, D. Vogt, J.W. Geus, J.G. Donkervoort. Top. Catal. 55 (2012)

109 C48 CATALYTIC CARBYLATI F LEFIS, ALCHLS AD BEZYL HALIDES I MLTE SALT MEDIUM.L. Eliseev, T.. Bondarenko, A.L. Lapidus.D.Zelinsky Institute of organic chamistry, Moscow, Russia Transition metal-catalyzed carbonylation of unsaturated hydrocarbons, alcohols and halides is a direct one-step route to carboxylic acids and esters. In presented work we systematically studied application of some molten salts such as tetrabutylammonium and 1-butyl-3-methylimidazolium derivatives as a media for these reactions. This approach provides a number of unusual possibilities. The most striking result is higher activity of phosphine-free palladium catalyst than that of traditional Pd-phosphine complexes. Bromide-containing molten salts stabilize palladium in the form of nano-sized suspension, as demonstrated by TEM. For unsymmetrical olefinic substrates, regioselectivity depends on anion nature in molten salt. In particular, chloride improves selectivity to 2-phenylpropanoic acid in carbonylation of styrene. Due to high solubility of catalyst in molten salt, it can be used repeatedly by simple extraction of products from reaction mixture with diethyl ether. In dodecene-1 carbonylation, ten cycles were carried out without loss of activity and selectivity. Importantly, reloading procedure may be performed in air atmosphere. Reaction scheme for the carbonylation of 1-phenylethanol into phenylpropanoic acids is proposed. Hydroxycarbonylation of benzyl halides in molten salt medium proceeds fast in the absence of base. Therefore, formation of stoichiometric amount of halide salt may be avoided. 109

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112 P1 SYTHESIS F FLURESCET RECEPTRS VIA Pd-CATALYZED AMIATI F 6-BRMQUILIE AD 3-BRMPHEATHRLIE A.S. Abel 1, A.D. Averin 1, A.G. Bessmertnykh-Lemeune 2, I.P. Beletskaya M.V. Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia 2 - Universite de Bourgogne, ICMUB, Dijon, France umerous works have been devoted to the design of new fluorescent sensors for various applications such as clinical toxicology, environmental bioorganic chemistry and waste management [1]. To develop optical molecular probes or sensors for toxic metals, ruthenium complexes with ditopic 1,10-phenanthrolines seem to be an appropriate solution. Moreover, aminoquinolines possess good fluorescent properties but have not yet been investigated as a signaling subunit in chemosensors. In this work, Pd-catalyzed amination of 6-bromoquinoline (1) and 3-bromo-1,10-phenanthroline (2) with linear polyamines 3a-d was investigated to prepare fluorescent receptors. The fluorescent derivatives of 6-aminoquinoline 4 were synthesized in good yields (up to 62%) using Pd/BIAP system as catalyst (Scheme). The amination of 3-bromo-1,10-phenanthroline is more complicated and Josiphos ligand should be used to obtain 3-amino-1,10-phenanthrolines 5 in satisfactory yields (32-36%) (Scheme). Scheme. Pd-catalyzed amination of 6-bromoquinoline (1) and 3-bromo-1,10-phenanthroline (2) This reaction is a key step in the synthesis of fluorescent receptors 6-8 (Figure). The sensing properties of receptors 7 and 8 in the presence of various amounts of environmentally-relevant metal ions were evaluated by UV-vis and fluorescent spectroscopy. Figure. Fluorescent receptors for metal ions. Acknowledgements: The work was performed in the frames of French-Russian Associated Laboratory LAMREM and financially supported by the RFBR (grant ) and CRS. [1] A.. Uglov, A.G. Bessmertnykh-Lemeune, R. Guilard, A.D. Averin, I.P. Beletskaya, Russ. Chem. Rev., 2014, 83,

113 P2 MECHAISM F CARB MXIDE XIDATI VER SUPPRTED Cu CATALYSTS Yu.A. Agafonov 1,.A. Gaidai 1,.V. ekrasov 1, L.C. Loc 2,. Tri 2, H.T. Cuong 2, H.S. Thoang 2, A.L. Lapidus Institute of rganic Chemistry, RAS, Moscow, Russia 2 - Institute of Chemical Technology, Vietnam Acad. Sci. Techn., Ho Chi Minh City, Vietnam Supported Cu catalysts with additives of other oxides are effective ones for C oxidation. Introduction of small amounts of noble metals in these catalysts allows to increase their activity which can exceed the activity of supported platinum catalysts the most active known ones in C oxidation. Designing new catalysts for this process requires depth knowledge on the reaction mechanism. This work is devoted to the study of mechanism of C oxidation over the following supported on -Al 2 3 catalysts: 10 (wt.) %Cu (CuAl), 10 %Cu+20% Ce 2 (CuCeAl), 10 %Cu+10% Cr 2 3 (CuCrAl) without and with addition of Pt. The content of Pt varied in the range of wt.%. The following physico-chemical methods were used for catalyst investigation: BET 2 -Adsorption, XRD, TPR, SEM, EDS and IR-C adsorption. There are the surface data of Table. Surface characteristics of the studied catalysts: specific surface area (S BET ), crystal size of Cu (d Cu ), dispersion of Cu (γ Cu ), maximum reduction temperature (T max ) and extent of reduction for ions Cu 2+ Catalysts (K, %) S BET m 2 /g d Cu nm γ Cu % T max C 113 studied catalysts in Table. It is seen that the Cr, Ce and Pt enhanced the reducibility of copper catalysts what expressed in the decrease of the reduction temperature and the increase of the reduction extent (the reducibility of catalysts CuAl and CuCeAl was increased in times). It was shown that the optimal Pt content is 0.1%. With this amount of Pt, catalyst PtCuCeAl was capable to convert completely C to C 2 at 110 o C (without Pt - at 125 o C). The process mechanism was studied by unstationary response method. Relaxation curves, describing a transition of the system to a new steady state, were obtained by a jump change of the corresponding concentrations. The residence time, defined as the ratio of the reaction system volume to the flow rate, was 2-5 times lower than the turnover time. It is meant that the observed transition phenomena were associated with the intrinsic processes. It was shown that Pt weakened the interaction of active phase which resulted in an increase of the reaction rate. The initial substances participated in the reaction in adsorbed state, the most part of the surface was occupied by oxygen over all the catalysts, Ce was facilitated the mobility of oxygen. Pt was increased the bond strengh of C, 2 and C 2 with the surface of catalysts. ot only adsorbed oxygen, but lattice oxygen took part in the reaction but the last oxygen in less extent. The change of introduced glass filler in the reactor showed that reaction of C oxidation proceeds mainly through heterogeneous mechanism, the share of homogeneous mechanism does not exceed 15%. It was shown that C and 2 adsorption were quick steps, one intermediate compound was formed in slow step of the process. The overall step-scheme of C oxidation was proposed over studied catalysts. The work is supported by RFBR ( _Viet_a) and AFSTED grant K Red % xide Catalysts CuAl CuCrAl CuCeAl Pt-containing oxide catalysts 0.1PtCuAl PtCuAl PtCuCrAl PtCuCeAl

114 P3 EFFICIET CATALYTIC HYDRDEXYGEATI F UPRTECTED CYCLIC IMIDES T CYCLIC AMIES BY HETERGEEUS CATALYSIS A.M. Maj, I. Suisse, F. Agbossou-iedercorn University Lille ord de France, UCCS UMR 8181 CRS, ESCL C7 CS90108, Villeneuve d Ascq Cedex, France Cyclic amines comprising fused saturated -heterocycles are valuable synthetic intermediates. They are found in numerous drug candidates such as bicifadine, cytisine, gliclazide, or telaprevir to name just a few (Figure 1). The catalytic hydrogenation of imides appears to be the most elegant and promising reaction to produce properly and efficiently such amines. Since the reaction might potentially lead to several compounds, it needs to be controlled by an appropriate catalyst, which has to perform selectively two successive reductive cleavages of the C= functionalities without breaking the cycle. H H H H H S H ptol H H H Bicifadine Cytisine Gliclazide Telaprevir H Figure 1. Bioactive cyclic amines. As part of our ongoing interest for the application of catalytic hydrogenation in the preparation of cyclic amines, [1] we became interested in the synthesis of fused -heterocycles. Herein, we report on the first efficient total reduction of nitrogen-unsubstituted cyclic imides in the presence of heterogeneous catalysts generated in situ from rhodium and molybdenum carbonyls (Scheme). Various substrates could be reduced with high selectivities and yields (both up to 100%). Platinum catalysts proved also efficient to hydrogenate some cyclic imides. In addition, all catalysts could be recycled at least three times without significant loss of activity. Finally, hydrodeoxygenation of a model cyclic imide was successfully performed on a gram scale. [2] ( ) n n = 0 or 1 H catalyst solvent PH 2, T H ( ) n H + ( ) n H + ( ) n H up to 100% yield References [1] a) Maj, A. M.; Suisse, I.; Méliet, C.; Agbossou-iedercorn, F. Tetrahedron: Asymmetry 2010, 21, b) Maj, A. M.; Suisse, I.; Méliet, C.; Hardouin, C.; Agbossou-iedercorn, F. Tetrahedron Lett. 2012, 53, c) Maj, A. M.; Suisse, I.; Hardouin, C.; Agbossou- iedercorn, F. Tetrahedron 2013, 69, [2] Maj, A. M.; Suisse, I.; Pinault,.; Robert.; Agbossou-iedercorn, F. ChemCatChem accepted. 114

115 P4 REACTIS F -ALKYLHALGEALDIMIES WITH,- DIALKYDITHIPHSPHRIC ACIDS.G. Aksenov, R.A. Khairullin, M.B. Gazizov, R.. Burangulova Kazan ational Research Technological University, Department of rganic Chemistry, Kazan, Russian Federation We found that direction of interaction of -alkyl-2-halogenaldimines (1-2) with О,Оdialkyldithiophosphoric acids (3) mainly depends on the nature of halogen. Reaction between О,Оdialkyldithiophosphoric acids (3) and -alkyl-2-chloroaldimines (1) was first studied by dynamic 1 Н, 13 С and 31 Р MR in the temperature intervals from -60 C to 25 С. It was found that reaction proceeds in two steps. At first step, which proceeds at -60 С, the protonation of imine nitrogen occurs and intermediate iminium salts are formed О,О-dialkyldithiophosphates - alkylchloroaldiminium (4). At the second step, which is observable at -5-0 С, the chlorine atom is substituted by О,О-dialkyldithiophosphate group. The final products of the reaction are chlorides of -alkyl-2-о,о-dialkyldithiophosphatopropaniminium (5). We propose that salt (4) is transfromed into product (5) through the intermediacy of salt (6) with delocalized azaallyl dication as a result of heterolytic dissociation of the bond tertiary carbon-chlorine. Synthetic result of the reaction of dithioacid (3) with -alkyl-2-bromoaldimine (2) is completely different as major products were obtained phosphorylsulfide (7) and iminium salt of unsubstituted aldimine (8). Thus, we for the first time discovered the reaction of reduction of organic bromine derivative (2) by О,О-dialkyldithiophosphoric acid. At temperatures С, 31 Р MR spectroscopy allowed to detect the formation of intermediate salt (9, δ 108 ppm). The work is supported by RFBR and the Government of Tatarstan, project _p povolzhe _а/2013 and Ministry of education and Science (task 2014/56 within the framework of basic part of stat task). 115

116 P5 METAL-FREE TRASAULATI REACTI F IDLES WITH ITRSTYREES: SIMPLE PRACTICAL SYTHESIS F QUILIE DERIVATIVES A.V. Aksenov 1,.A. Aksenov 1, I.V. Aksenova 1, A.. Smirnov 1, M. Rubin Department of Chemistry, orth Caucasus Federal University, Stavropol, Russian Federation 2 - Department of Chemistry, University of Kansas,Lawrence, USA A convenient metal-free method for preparation of a large variety of 3-aryl- and 3-alkylsubstituted 2-quinolones 4, as well as 2,3-disubstituted quinolines, was proposed. This approach involves previously unknown transannulation of 2-substituted indoles 1 in the reaction of β-nitrostyrenes 2 in polyphosphoric acid. The method is based on the ring-expansion of the pyrrole cycle in indoles upon attack of amphyphilic reagents at the enamine double bond. H 1 R 1 R 3 R 2 + R 1 R P( )( H ) R P( )( H ) 2 R 2 2 H 4 R 1 P P A - H + R 3 + R 1 H + R 2 R 3 R 3 R 1 R 1 P( )( H ) 2 R 2 H P( )( H ) 2 H 2 R 3 H + + H P R 2 R 1 R 2 R 3 R 3 R 1 R 1 H H R 2 H P( )( H ) 2 R 3 R 2 H P H R 1 R 3 R 2 R 3 H R 1 H P( )( H ) 2 R 1 = H, Me ; R 2 = Ph, Me; R 3 = Ph, 4-MeC 6 H 4, 4-iPr-C 6 H 4, 3,4-Me 2 C6H 3, 4-EtC 6 H 4,2-FC 6 H 4, 3,4- Cl 2 C 6 H 3, 3-BrC 6 H 4, n-pr Introduction of an alkyl substituent into β-position of β-nitrostyrene 6 renders formation of quinoline 7 as major product. The mechanism of this transformation is identical to the one shown above, but includes elimination of water and aromatization at the last step. H R 2 R R 3 H 2 R R 2 = Ph, Me; R 3 = Ph, Ph. Convenient and general metal-free approaches to 3-aryl and 3-alkyl-substituted 2-quinolones, as well as to 2,3-disubstituted quinolines were developed, which included the previously unknown process of transannulation of 2-substituted indoles in the reaction with β-nitrostyrenes in polyphosphoric acid. The reaction was also efficiently combined into a cascade with a Fisher indole synthesis. Unlike most other known methods, the described protocol utilizes readily available starting materials. Unique properties of PPA, serving as a mild proton donor, source of efficient leaving group (or temporary protecting group), water scavenger and high boiling solvent makes it an ideal media for the described transformation. This work was carried out with financial support from the RFBR (grant ) R 2 H P H 116

117 P6 MECHACHEMICAL SYTHESIS F CHRMIUM CARBXYLATES AD THEIR CATALYTIC PRPERTIES I ETHYLEE TRIMERIZATI K.A. Alferov 1, L.A. Petrova 2, V.D. Makhaev 2, G.P. Belov Institute of Problems of Chemical Physics RAS, Department of Polymers and Composite Materials, Chernogolovka, Russian Federation 2 - Institute of Problems of Chemical Physics RAS, Department of Functional Inorganic Materials, Chernogolovka, Russian Federation Selective synthesis of individual alpha olefins (1-butene, 1-hexene, 1-octene) is an urgent problem because these compounds are widely used for the production of ethylene copolymers, plasticizers, lubricants, etc. [1, 2]. ne of the most efficient systems for ethylene trimerization is a system based on chromium tris(2-ethylhexanoate) (Cr(EH) 3 ), 2,5-dimethylpyrrole and organoaluminum compounds. Methods for the synthesis of Cr(EH) 3 based on reactions in solutions are quite laborious and lingering. The products obtained by the methods are sticky and unhandy. The operations for the isolation and purification of the product complicate its production [3, 4, 5]. owadays, green chemistry seems as a very promising research area, so the processes of solventfree solid reactant interactions attract much attention. We have developed a method for the synthesis of Cr(EH) 3 based on the solvent-free mechanochemical interaction of solid CrCl 3 and aeh with subsequent heating of the reaction mixture [6]. Physicochemical properties of the reaction products and mechanically activated CrCl 3 -aeh mixtures at different CrCl 3 /aeh ratios were investigated by IR-spectroscopy, XRDA and DCS. The solid phase interaction of CrCl 3 and aeh occurs in two main stages: 1) the reagents mixture mechanical activation resulting in their dispersion and mixing at the molecular or cluster level; and 2) thermally initiated exothermic interaction of the activated reactants to give the final products. The use of the method makes it possible to shorten the process duration appreciably. The obtained reaction mixtures and isolated Cr(EH) 3 as well as commercially available Cr(EH) 3 (8-10 % wt. in mineral spirits) were tested as components of the Cr(EH) 3 /2,5- dimethylpyrrole/alet 3 /CCl 4 catalytic system for ethylene trimerization. The productivity and selectivity of the catalyst based on Cr(EH) 3 synthesized by the mechanochemical method were similar to the results obtained for the commercial Cr(EH) 3. Moreover, reaction mixtures produced directly after the synthesis of Cr(EH) 3 also form an active catalyst for ethylene trimerization. Syntheses differed in the time of mechanochemical activation (1-4 h) and reagent ratio (aeh/crcl 3 = ) were also performed. The catalytic systems based on thus obtained reaction mixtures demonstrated close values of productivity (11-13 kg/(g Cr h)) and selectivity (1-С 6 = % wt., C 8+ = % wt., PE = 0,1-0,3 % wt.) in ethylene to 1-hexene trimerization. The study was in part financially supported by the Russian Foundation for Basic Research (project no a) and by the Presidium of the Russian Academy of Sciences Basic research Program 3. [1] Dixon J.T., Green M.J., Hess F.M., Morgan D.H. J. rganomet. Chem. 689(23) (2004). [2] McGuinness D. S. Chem. Rev. 111(3) (2011). [3] Briggs J.R. US (Union Carbide Corporation), March 14, [4] Knudsen R.D. et al. US 2007/ A1 (Chevron Phillips Chemical Company), August 19, [5] Sydora.L. et al. US 2013/ A1 (Chevron Phillips Chemical Company), December 12, [6] Rus. Patent Application /20(088111) (IPCP RAS), December 20,

118 P7 EFFECT F CHEMICAL STRUCTURE F VILGE-DERIVATIVES AS A ARTIFICIAL C-EZYME THE CARB DIXIDE REDUCTI ACTIVITY F FRMATE DEHYDRGEASE Y. Amao 1, S. Ikeyama saka City University,Advanced Research Institute for atural Science and Technology, saka,japan 2 - saka City University,Graduate School of Science, saka,japan Many studies on electro-catalyzed C 2 reduction have been performed using specific electrode materials. n the other hand, studies on C 2 fixation also have investigated photocatalysis on semiconductors such as titanium dioxide, silicon carbide and strontium titanate. However, these systems use ultraviolet irradiation and the total reaction is low yield, whereas highly efficient C 2 fixation system using visible light is more desirable. We previously reported a system for visible light-induced methanol synthesis from C 2 with the system formate, aldehyde, and alcohol dehydrogenases, and methylviologen (MV 2+ ) photoreduction by the visible light photosensitization of water soluble zinc porphyrin in the presence of an electron donor in aqueous media. n this system, the reduced form of methylviologen (MV.+ ) is used as an artificial co-enzyme for these dehydrogenases. To improve the yield for methanol production from C 2, conversion of C 2 to formic acid with formate dehydrogenase (FDH) and reduced formed viologen is most important step. In this work, some artificial co-enzymes with 4,4 - bipyridine skeletons as shown in Figure 1 are synthesized and effect of chemical structures of artificial co-enzymes on the activity of the reduction of C 2 to formic acid with FDH are investigated. The conversion of C 2 to formic acid with FDH and one-electron reduced form of artificial co-enzyme was carried out as following method. The sample solution containing 3.0 µmol of artificial co-enzyme, 5.7 mmol of sodium dithionate, and FDH (10 units) in 3.6 ml of C 2 saturated sodium pyrophosphate buffer (ph 7.4) at 30.5 C for 1 min. The formic acid concentration produced is measured by ionic chromatography. Figure 1. Chemical structures of viologen-derivatives as artificial co-enzymes for formate dehydrogenase By using MV 2+ as the reference, the formic acid production increased by using cationic artificial coenzymes (H 2 H 2 CH 2 C-V-CH 2 CH 2 H 2 and CH 3 -V-CH 2 CH 2 H 2 ). n the other hand, the HCH production decreased by using anionic co-enzymes (HCH 2 C-V-CH 2 CH and CH 3 -V- CH 2 CH). The production of formic acid in this reaction depends on chemical structures of artificial co-enzymes. Among the artificial co-enzymes, H 2 H 2 CH 2 C-V-CH 2 CH 2 H 2 has high affinity for FDH compared with the other compounds. 118

119 P8 Cu(I)-CATALYZED ARYLATI F BILGICALLY ACTIVE DI- AD PLYAMIES A.D. Averin, M.V. Anokhin, S.P. Panchenko, I.P. Beletskaya M.V. Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia Di- and polyamines like putrescine, cadaverine, spermidine and spermine were chosen for the studies of their Cu(I)-catalyzed, -diarylation for the synthesis of new compounds with diverse biological activity. Arylation was carried out using iodobenzene, 4-fluoroiodobenzene, 4- (trifluoromethyl)iodobenzene and 4-iodobiphenyl. The reactions of butane-1,4-diamine were successfully catalyzed with either CuI/L1 (L1 = L-proline) or CuI/L2 (L2 = 2- isobutyrylcyclohexanone) systems while pentane-1,5-diamine demonstrated better results with CuI/L2 system. Cs 2 C 3 was taken as a base in all cases. Selective 1, 3 -diarylation of triamine and 1, 4 -diarylation of tetraamine turned to be a more complicated task, and target compounds were obtained in moderate yields using CuI/L2 catalytic system. Acknowledgement: The work was financially supported by the RFBR grant

120 P9 ITRATIG AD ITRSATIG REAGETS I VEL HETERCYCLIZATI REACTIS. READY ACCESS T HIGHLY SUBSTITUTED PYRIMIDIE AD ISXAZLE DERIVATIVES E.B. Averina, K.. Sedenkova, D.A. Vasilenko, T.S. Kuznetsova,.S. Zefirov Lomonosov Moscow State University, Department of Chemistry Recently we have elaborated novel synthetic approaches to five- and six-membered - and,heterocycles basing on the heterocyclization of electrophilic alkenes or three-membered carbocycles under the treatment with nitrating or nitrosating reagents. The reaction of tetranitromethane with electrophilic alkenes in presence of triethylamine was found to afford 5-nitroisoxazoles 1 highly reactive and versatile compounds which may be used as precursors of diverse functionalized compounds [1]. Employing the reduction of nitroisoxazoles 2 we suggested the regioselective method of synthesis of 5-aminoisoxazoles 2 that was used to accomplish a structure design of biologically active compounds. The series of compounds 2 was obtained in good yields (50-90%) and their antiviral activity was investigated. A series of previously unknown 4-fluoropyrimidine 1-oxides 4 was obtained via three-component heterocyclization involving gem-bromofluorocyclopropanes 3, nitrosating or nitrating agent and organic nitrile [2]. Preparative method of synthesis of 4-fluoropyrimidines 5 from corresponding - oxides under the treatment with PCl 3 was elaborated. EWG 1 SnCl 2 EWG R 2 EtH 2 R 2 2 H 2 C( 2 ) 4 -Et 3 R 1 = EWG (C()R', C 2 R", P()(Et) 2 2, C 2 R"); R 2 = H, Alk R 1 R 2 :CBrF R 1 R 2 R,R 1,R 2 : Alk, Ar; [ + ]: BF 4, 2 BF 4, 2 Tf R 1 R 1 R 2 F F [ + ] Br RC R Fluorosubstituted pyrimidine -oxides 4 and pyrimidines 5 demonstrate high reactivity in aromatic nucleophilic substitution with various -, -, P-nucleophiles. In particular, a series of 4- aminopyrimidines and pyrimidine -oxides, potent as compounds with antiviral activity, was obtained via this reaction. In conclusion, simple and efficient synthetic methods allowing polyfunctionalized isoxazoles, pyrimidines and pyrimidine -oxides, including those with valuable properties, from readily available starting materials were developed. We thank the Russian Foundation for Basic Research (Projects mol_а, a) and Presidium RAS (program 8P) for financial support of this work. [1] (a) Y.A. Volkova, E.B. Averina, Y.K. Grishin, P. Bruheim, T.S. Kuznetsova,.S. Zefirov J. rg. Chem., 2010, 75, ; (b) E.B. Averina, Y.A. Volkova, Y.V. Samoilichenko, Y.K. Grishin, V.B. Rybakov, A.G. Kutateladze, M.E. Elyashberg, T.S. Kuznetsova,.S. Zefirov Tetrahedron Lett., 2012, 53, [2] (a) K.. Sedenkova, E.B. Averina, Yu.K. Grishin, A.G. Kutateladze, V.B. Rybakov, T.S. Kuznetsova,.S. Zefirov J. rg. Chem., 2012, 77, ; (b) K.. Sedenkova, E.B. Averina, Yu.K. Grishin, T.S. Kuznetsova,.S. Zefirov Tetrahedron Lett., 2014, 55, F 5 R PCl 3 R 120

121 P10 TRASFER HYDRGEATI F ACETPHEE VER BIS-IMIE RHDIUM(I) CMPLEX. DFT STUDY.M. Badyrova 1, Z. Lin 2, L.. indakova Irkutsk State Technical University, Physical and Technical Institute, Irkutsk, Russia 2 - The Hong Kong University of Science and Technology, Department of Chemistry, Hong Kong (P. R. China) There are two reaction mechanisms for asymmetric transfer hydrogenation reactions of ketones over a diamine rhodium(i) complex leading to optically active secondary alcohols: a stepwise process through an intermediate hydride complex derived from an alkoxy complex via -hydride elimination and a concerted process where the hydrogen is directly transferred from the alkoxy complex to the coordinated substrate [1]. Here, we investigated mechanism of hydrogen transfer reaction (Scheme 1) from 2-propanol to acetophenone over a bis-imine-rhodium(i)-chloride complex with optical active bis imine ligand R,R-1 on the basis of DFT theoretical calculations. Scheme 1 Based on the mechanism proposed by Guiral et al [1], we designed a catalytic cycle (Scheme 2). This cycle starts with the hydride complex 1. The first step is reversible dissociation of a Rh- bond in the 18-electron hydride complex leading to a 16-electron intermediate (the hydride complex 2). From 2, there are two possible pathways to achieve hydride transfer to acetophenone, an external pathway vial 3a and an internal pathway via 3b (Scheme 2). Both the two hydride transfer pathways give the alkoxy complex 4, which leads to 5 after with a metathesis with 2-propanol to release the product molecule. ext step involves -H elimination to give 6 followed by release of the sideproduct (acetone) to regenerate the starting hydride complex 1. H Rh (CH 3 ) 2 C Rh 1 2 H H 3 C CH 3 H C Rh Rh Rh Scheme Geometry optimizations of all species have been performed by means of the DFT M06 hybrid method [2]. The 6-31G(d) basis set was chosen to describe C,,, H atoms and the LanL2DZ basis set was used for Rh. All of the calculations were performed with the Gaussian 09 program [3]. 1. Guiral V., Delbecq F., Sautet P. rganometallics, 2000, 19, Zhao Y., Truhlar D. G., Theor Chem Account, 2008, 120, Frisch, M. J.; et al. Gaussian 09, Revision A.1; Gaussian Inc., Wallingford, CT, Rh 3a H Rh 3b H 3 C H CH 3 C H 3 C C Ph Ph CH CH 3 4 H 3 C CH Ph (CH 3 ) 2 CHH (CH 3 )PhCHH 121

122 P11 RHDIUM(II) CATALYZED REACTIS FR SYTHESIS F VEL AD DIVERSE FUR[2,3-D]PYRIMIDIEDIES AD THIXFUR[2,3-D]PYRIMIDIEES E.R. Baral, K.B. Somai Magar, Y.R. Lee School of Chemical Engineering, Yeungnam University, Gyeongsan , Republic of Korea Furopyrimidines, the derivatives of pyrimidine and analog of purine have been demonstrated to have antimalarial, antifolate, antitumor, antiviral, antibacterial and antifungal, and antihypertensive properties. 1-2 Accordingly, several methods have been devised to synthesize furopyrimidines. 3-4 The general methods for the synthesis of furo[2,3-d]pyrimidinediones by ceric ammonium nitrate mediation involving ionic (non-carbenoid) mechanism is limited with the substrate scope in terms of olefins and alkynes with low yields, 5 while three component reactions of, -dimethylbarbituric acid with benzaldehydes, and isocyanides, provided 2,3-disubstituted furans. 6 However, there is a need for more convenient and efficient synthetic methods for the preparation of furo[2,3- d]pyrimidinedione derivatives, and in particular, the synthesis of thioxofuro[2,3-d]pyrimidinedione derivatives has not been reported to date. In this conference, we present the rhodium (II)-catalyzed reactions of cyclic diazo compounds derived from barbituric acid or thiobarbituric acid with arylacetylenes and styrenes. These reactions provide a rapid synthetic route to the preparation of a variety of novel and diverse furo[2,3- d]pyrimidine-2,4-diones, 2-thioxodihydrofuro[2,3-d]pyrimidin-4-ones, dihydrofuro[2,3- d]pyrimidine-2,4-diones, and 2-thioxotetrahydrofuro[2,3-d]pyrimidin-4-ones. R X Y' R Y' Rh 2 (Piv) 4 toluene reflux R X R X=, S R=Me, Et 2 Y Rh 2 (Piv) 4 PhF rt - 60 o C R X Y R References 1. G. Jähne, H. Kroha, A. Müller, M. Helsberg, I. Winkler, G. Gross, T. Scholl, Angew. Chem. Int. Ed. Engl. 1994, 33, Q. Dang, Y. Liu, M. D. Erion, J. Am. Chem. Soc. 1999, 121, A. Sniady, M. D. Sevilla, S. Meneni, T. Lis, S. Szafert, D. Khanduri, J. M. Finke, R. Dembinski, Chem. Eur. J. 2009, 15, A. Sniady, A. Durham, M. S. Morreale, A. Marcinek, S. Szafert, T. Lis, K. R. Brzezinska, T. Iwasaki, T. hshima, K. Mashima, R. Dembinski, J. rg.chem. 2008, 73, K. Kobayashi, H. Tanaka, K. Tanaka, K. Yoneda, Synth. Commun. 2000, 30, M. B. Teimouri, R. Bazhrang, Bioorg. Med. Chem. Lett. 2006, 16,

123 P12 DUAL REACTIVITY F TRAREES I [4+2]-CYCLADDITI REACTIS M.A. Bastrakov, A.M. Starosotnikov, S.A. Shevelev.D. Zelinsky Institute of rganic Chemistry RAS, Laboratory of itrogen-containing Aromatic Compounds, Moscow, Russia [4+2]-Cycloaddition is one of the fundamental protocols for the construction of a new ring, which accompanies the formation of two bonds. This reaction is known for nitroalkenes 1a, as well as for few highly electrophilic (low aromatic) benzoazoles 1b-c. These compounds readily undergo Diels- Alder reactions at C-C double bond activated by the nitro group. Also they form anionic σ-adducts with very weak nucleophiles 1b. As a part of our research on highly electrophilic heterocyclic systems we have found that 4,6- dinitroanthranil reacts with dienes and nucleophilic dienophiles in mild conditions 2. Moreover we have proposed methods for the synthesis of new policyclic heteroaromatic compounds on the nitroarenes basis consisting in annelation of a furoxan ring to different dinitrobenzoazoles and azines 3. Some of these compounds readily undergo [4+2]-cycloaddtition with dienes and dienophiles. This work was supported by the Russian Foundation for Basic Research, Projects o , mol_a and Grant of the President of the Russian Federation for State Support to young Russian scientists, Grant MK (a) S.E. Denmark, A. Thorarensen, Chem Rev., 1996, 96, 137; (b) S. Lakhdar, R. Goumont, T. Boubaker, M. Mokhtari, F. Terrier, rg. Biomol. Chem., 2006, 4, 1910; (c) S. Kurbatov, R. Goumont, S. Lakhdar, J. Marrot, F. Terrier, Tetrahedron, 2005, 61, 8167; 2. A.M. Starosotnikov, M.A. Leontieva, M.A. Bastrakov, A.V. Puchnin, V.V. Kachala, I.V. Glukhov, S.A. Shevelev, Mendeleev Commun, 2010, 20, M.A. Bastrakov, A.M. Starosotnikov, I.V. Glukhov, S.A. Shevelev, Russ. Chem. Bull. Int. Ed., 2009, 58,

124 P13 UEXPECTED FRMATI F -ALKYLIMIDES I REACTI F MALEPIMARIC AD CITRACPIMARIC ACIDS WITH SECDARY AMIES M.P. Bei 1, A.P. Yuvchenko 1, A.V. Baranovsky The Institute of Chemistry of ew Materials, 36 F.Skoriny st., Minsk , Belarus 2 - The Institute of Bioorganic Chemistry, 5/2 Kuprevich st., Minsk , Belarus The Diels-Alder reaction of levopimaric acid with active dienophiles produces adducts (maleo-, fumaro-, quinopimaric acids) which are useful precursors in the synthesis of chiral ligands, terpenoquinones, biologically active compounds. Recently, we have reported the synthesis of isomer of citraconopimaric acid (2), an analog of well-known maleopimaric acid (1), bearing methyl group at C The method includes preparation of the adduct of pine rosin with citraconic anhydride (formed in situ from itaconic acid) followed by recrystallization of the product from carbon tetrachloride and benzene. We have initiated the investigation of the reaction of citraconopimaric acid (2) with some secondary aliphatic amines in order to study the steric influence of the CH 3 group at C-15 of the acid (2) on regioselectivity of anhydride ring opening by nucleophilic agents. It was established that the heating of citraconopimaric acid (2) solution in diethylamine, dipropylamine in autoclave, dibutylamine at 135ºC for 30h leads to the formation of -ethyl-, -propyl-, -butylimides of citraconopimaric acid (3 5). Unlike citraconopimaric acid (2), reactions of maleopimaric acid (1) with diethyl-, dipropylamine at 135ºC gave -ethyl-, -propylimides of maleopimaric acid (6, 7; yields 60 80%) and amidodiacids (9, 10; yields 10 15%), and the reaction with dibutylamine gave only maleopimaric acid -butylimide (8). 2 R' + CH R' = H (1), CH 3 (2) R 2 H 135 o C R' = CH 3 R' = H 124 R CH (3, 4, 5) R = C 2 H 5 (3), n-c 3 H 7 (4), n-c 4 H 9 (5) CH CH R R 2 + (6-8) CH (9, 10) * R = C 2 H 5 (6, 9), n-c 3 H 7 (7, 10), n-c 4 H 9 (8) * The exact structure of regioisomer is not established The formation of -alkylimides (3 8) in the above transformations could be result of a thermal degradation of intermediate amidoacids giving stable cyclic imides. Would this assumption be true, the formation of mixture of two imides should be observed in the reaction of acids (1, 2) with unsymmetrical secondary amines. Thus, when acids (1, 2) were treated with methyl- or ethyl-(2-hydroxyethyl)amine, the formation of a mixture of two imides indeed was observed. 2 (1, 2) H 135 o C R + R R' + H R' CH CH R = CH 3, C 2 H 5, R' = H, CH 3 [1] M.P. Bei, A.P. Yuvchenko. Patent of the Republic of Belarus 13,646, [2] M.P. Bei, A.P. Yuvchenko, A.V. Baranovsky. Proceed. at. Acad. Sci. Belarus. 2013, 4, 104 H

125 P14 SYTHESIS F TRYPTAMIES FRM CYCLPRPYLKETES ARYLHYDRAZES AD THEIR BILGICAL STUDIES A.Yu. Belyy 1, R.F. Salikov 2, Yu.V. Tomilov Higher Chemical College of Russian Academy of Sciences 2 -. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences Tryptamine derivatives are psychoactive compounds and are widely used as 5-HT agonists. We have found that cyclopropyl methyl ketone hydrazones rearrange into a mixture of tetrahydropyridazines and tryptamines, the best yield of tryptamine being observed in the case of generated in situ bromophenylhydrazone. The rearrangement of cyclopropyl ketones with a bulky group in most cases gives tetrahydropyridazines exclusively. The tryptamine derivatives obtained demonstrated their antitumor activity against human neuroblastoma cell line SH-SY5Y. The best result was shown by 2-methyl-5-bromotryptamine (IC 50 = 5,06 µм) with the therapeutic index of 4, determined from the toxicity against human embryonic kidney cells (HEK 293). In order to investigate the biological activity of this interesting class of compounds we derived the tryptamines in three different ways: substitution of bromine, indole nitrogen alkylation and primary amine nitrogen. The biological studies are under performance. 125

126 P15 DEHYDRGEATI F LW ALIPHATIC ALCHLS CPPER SUPPRTED STRUCTURED CATALYST D.A. Bokarev 1, E.A. Ponomareva 2, E.V. Egorova D. Zelinsky Institute of rganic Chemistry RAS, Moscow, Russia 2 - Lomonosov Moscow State University of Fine Chemical Technologies, Moscow, Russia The important direction of the chemical industry development is engineering of new alternative manufactures based on renewable sources of raw materials. These materials could be methanol and ethanol, especially applied for synthesis of methylformiat and acetaldehyde respectively. 2CH 3 H HCCH 3 +2H 2 C 2 H 5 H CH 3 CH +H 2 To realize the process of dehydrogenation with high technical parameters new catalytic systems must be worked out. Recently new classes of heterogeneous catalysts based on structured carbon fibers were developed. They possess a number of advantages - homogeneous distribution of a stream, low pressure drop. Moreover, fibers structured catalysts offer flexibility and endless forms that allow using them in reactors of a various constructions. It was shown that 5 wt.% of copper supported by impregnation appeared to be optimal in the process of alcohol dehydrogenation. Compared to powder and granular carbon materials used earlier, catalysts based on structural carbon fibers showed higher activity and selectivity due to better distribution of active component on the surface of the carrier (fig.1). Activity 126 g MeH /g Cu *h and 237 g EtH /g Cu *h Activity 24 g MeH /g Cu *h and 68 g EtH /g Cu *h Fig. 1. Distribution of copper particles on the surface of carbon structured fiber (left) and granular carbon material Sibunit (right) Thus, application of structured carbon fibers as a support of copper catalytic system leads to increase of activity in comparison with known literature data. That allows to make a conclusion about appropriateness of using it in the process of dehydrogenation of low aliphatic alcohols. 126

127 P16 ARYLAMIATI F 1,3,7-TRIAZAPYREES I.V. Borovlev,.P. Demidov,.A. Saigakova, G.A. Amangasieva orth Caucasus Federal University, Department of Chemistry, Stavropol, Russia In our previous reports we have shown that 1,3,7-triazapyrene displays peculiar properties due to the unique fusion of the carbocyclic and heterocyclic rings. Specifically these properties include the unusual ease of oxidative nucleophilic substitution of hydrogen, such as amination [1] and alkylamination [2], which proceed in aqueous media. The aim of this work is the synthesis of arylamino derivatives of this heterocycle. In spite of a common mechanism, the conditions mentioned above are not suitable for arylamination reaction due to the low nucleophilicity of aryl amines and their high sensitivity towards oxidation. This is why S H -arylamination reactions are still rare. We have found that the interaction of 1,3,7-triazapyrenes 1 with an excess of sodium arylamides obtained in situ in absolute DMS proceeds at room temperature to form the 6-aryl(hetaryl)amino- 1,3,7-triazapyrenes 2 in % yields. It was shown that the decisive factor for rearomatization of σ H -adducts is crucial access to the air oxygen. R R 1. A r H - a + D M S, R T, 2 2. H 2 X 1 2 R = H, Me; X = H, Ar, R 2 Under the same conditions (DMS, room temperature) the reaction of the rather accessible 6,8- dialkoxy-1,3,7-triazapyrenes 3 with sodium aryl amide has resulted to a product of nucleophilic ipso substitution of one of the two R groups - 6-alkoxy-8-aryl(hetaryl)amino-1,3,7-triazapyrenes 4. X H A r 1. A r H - a + D M S, R T 1. A r H - a + reflux ing toluene 2. H 2 2. H 2 R 4 H A r R 127 R A r H 3 5 R = Me, Et Products of double ipso substitution 6,8-bis(aryl(hetaryl)amino)-1,3,7-triazapyrenes 5 were synthesized by refluxing of the compounds 3 with excess of the sodium arylamides in toluene for a long time. Consecutively replacing one methoxy group in 6,8-dimethoxy-1,3,7-triazapyrene in DMS, and the second - in toluene, we obtained asymmetrically substituted diamine - 6- phenylamino-8-(pyridin-4-ylamino)-1,3,7-triazapyrene. This project received financial support from the Ministry of Education and Science of the Russian Federation in the framework of the State Assignment to the Higher Education Institutions /K. [1].. P. Demidov, I. V. Borovlev,. A. Saigakova,. A. emykina,. V. Demidova, and S. V. Pisarenko, Khim. Geterotsikl. Soedin., 142 (2011). [Chem. Heterocycl. Compd., 47, 114 (2011).] [2]. I. V. Borovlev,. P. Demidov,. A. Saigakova, S. V. Pisarenko,. A. emykina, J. Heterocycl. Chem., 48, o. 5, 1206 (2011). H A r

128 P17 SUSTAIABLE APPRACHES FR RGAIC SYTHETIC PRCESSES L.C. Branco, K. Zalewska, G. Carrera, M.. Da Ponte REQUIMTE, Departamento de Quнmica, Faculdade de Ciкncias e Tecnologia, Universidade ova de Lisboa, Caparica, Portugal For many synthetic approaches the incorporation of C 2 as alternative reagent or green solvent can improve significantly the efficiency (yields, purity, reaction conditions) for several organic processes. In recent years, the use and capture of Carbon Dioxide (C 2 ) became a hot research topic including their application for organic and pharmaceutical chemistry. 1 The possibility to use carbon dioxide as useful reagent for different synthetic approaches or supercritical C 2 for efficient extraction and separation processes has been reported. 1 The combination of ionic liquids and supercritical fluids has been reported for many organic transformations in particular catalytic reactions. 2 The possibility to use scc 2 in order to extract the pure products without IL or catalyst contamination is one of the advantages for these processes. Several publications proof the advantages for ILs and scc 2 combinations in order to recycle the catalytic media during many reaction cycles without loss of efficiency. In this communication, we described the applicability of carbon dioxide approaches in two different organic synthetic processes: 3 a) The use of C 2 as reagent for the preparation of reversible chiral and non-chiral carbamate salts by the reaction with different amines (e.g. primary alkyl and aryl amines or polyamines), aminoacids and pharmaceutical compounds in the presence of an organic superbase (e.g. DBU or tetramethylguanidine). According with the optimized reaction conditions, it s possible to tune the chemical and thermal stability as well as potential application of the final salts. b) The potential use of scc 2 for extraction and separation processes in the case of three asymmetric catalytic reactions in the presence of ionic liquids and/or chiral ionic liquids as solvent or chiral media respectively. In particular, Sharpless asymmetric dihydroxylation of olefins (in the presence of osmium catalyst), asymmetric Aldol and Michael reactions (in the presence of chiral organocatalysts based on chiral ILs) will be presented. The peculiar properties of carbon dioxide including as supercritical fluid open excellent perspectives for the application in novel organic synthetic transformations as well as their use in industrial processes. Acknowledgements: We thank the Fundação para a Ciência e Tecnologia for financial support (PEst-C/EQB/LA0006/2011 and PTDC/CTM/103664/2008 projects and SFRH/BD/67174/2009 for KZ PhD grant). References: 1. a) Goodrich, B. F.; de la Fuente, J. C.; Gurkan, B. E.; Zadigian, D. J.; Price, E. A.; Huang, Y; Ind. Eng. Chem. Res. 2011, 50, 111. b) Camper, D.; Bara, J. E.; Gin, D. L.; oble, R. D.; Ind. Eng. Chem. Res. 2008, 47, Afonso, C. A. M.; Branco, L. C.; Candeias,. R.; Gois, P. M. P.; Lourenço,. M. T.; Mateus,. M. M.; Rosa, J..; Chem. Commun. 2007, a) Carrera, G. V. M.; da Ponte, M..; Branco, L. C.; Tetrahedron, 2012, 68, b) Branco, L. C.; Serbanovic, A.; da Ponte, M..; Afonso, C. A. M.; ACS Catalysis 2011, 1, c) Carrera, G. V. S.M.; Costa, A.; Ponte, M..; Branco, L.C., Synlett 2013, 24,

129 P18 1 H AD 13 C ASSIGMETS F THREE SERIES BIACTIVE IMIDAZ[2,1-B]THIAZLE DERIVATIVES A.S. Bunev, E.V. Sukhonosova, G.I. stapenko, P.P. Purygin Togliatti State University, Togliatti, Russia The complete 1 H and 13 C MR assignments of three series bioactive imidazo[2,1-b]thiazoles were achieved by combination of one and two-dimensional MR experiments, and the MR signals of these compounds were analyzed and compared. The authors are grateful to the Ministry of Education and Science of the Russian Federation (State job o. 426) 129

130 P19 SYTHESIS F 1,4,5-TRISUBSTITUTED IMIDAZLES CTAIIG TRIFLURMETHYL GRUP A.S. Bunev, M.A. Vasiliev, G.I. stapenko, V.E. Statsyuk Togliatti State University, Togliatti, Russia A new synthetic protocol for the synthesis of 1,4,5-trisubstituted imidazoles (2a-i) containing trifluoromethyl group has been developed using van Leusen reaction, which incorporates twocomponent condensation reaction trifluoroacetimidoyl chlorides (1a-i) with tosylmethylisocyanide. This protocol provides a novel and improved method for obtaining trifluoromethyl containing 1,4,5- trisubstituted imidazoles in good yields. The authors are grateful to the Ministry of Education and Science of the Russian Federation (State job o. 426) 130

131 P20 THE QUATUM-CHEMICAL STUDY F THE KEY STEP F THE CYCLIZATI F 4,11-DIMETHXY-5,10-DIX-2- ATHRA[2,3-B]- FURA-3-CARBXYLATES E.E. Bykov, A.S. Tikhomirov, A.E. Shchekotikhin, M.. Preobrazhenskaya Gause Institute of ew Antibiotics RASM, Moscow, Russia Highly active inhibitors of topoisomerase I, capable of blocking the growth of tumor cells with activated mechanisms of multiple drug resistance, were discovered in the series of derivatives 4,11- dihydroxy-5,10-dioxoanthra[2,3-b]furan-3-carboxylic acids [1]. Previously, a scheme of preparation of 2-substituted derivatives of 4,11-dimethoxy-5,10-dioxoanthra[2,3-b]furan-3-carboxylic acids was developed. However yields of anthrafurandiones by this method seriously depended on a substituent in position 2 [2]. To understand this, a quantum-chemical estimations of the key step of the intermolecular cyclization of the intermediate enol forms of ethyl 2-(3-bromo-1,4-dimethoxy-9,10- dioxo-9,10-dihydroanthracene-2-yl)-3-hydroxypropanoates 1a-c to the corresponding anthra[2,3- b]furan-5,10-diones 2a-c were carried out. The quantum-chemical calculations by DFT method B3LYP/6-31+G(d) by means program package Gaussian-09 [3] confirmed that the activation barriers (ΔE # ) of cyclization of enol form 1a-c depend on the nature of the substituent R. The groups R that have different electronic properties influence actively on the electron density of the internal nucleophile what is enolic oxygen atom (see Table, Q and Ε HM ). The calculated values of ΔE # correlate with the yield of the anthra[2,3- b]furan-5,10-diones 2a-c [2]. Thus quantum-chemical evaluation of the key step of cyclization confirmed that the electron-withdrawing substituents reduce the reactivity of enol intermediates 1ac in the cyclization to the corresponding anthra[2,3-b]furan-5,10-diones 2a-c. Table. Parameters for the reaction of cyclization of anthra[2,3-b]furan-5,10-diones 2a-c. Derivative 2a 2b 2c R -CH 3 -Ph -CF 3 ΔE #, (kcal/mol) Ε HM, (ev) Q The yield, % [2] References 1. Shchekotikhin, A. E. et. al, Patent RU (2011). 2. Tikhomirov, A. S.; Shchekotikhin, A. E.Chem. Heterocycl. Compd. 2014, 50,

132 P21 MACRPLYCYCLIC CMPUDS CMPRISIG DIAZACRW ETHER MIETIES AD FLURPHRE GRUPS.M. Chernichenko, A.D. Averin, I.P. Beletskaya M.V. Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia Macrobicyclic compounds comprising structural fragments of diazacrown ethers and oxadiamines were synthesized using Pd-catalyzed amination reactions using Pd(dba) 2 /BIAP system [1]. They were further modified with various fluorophore substituents using catalytic and non-catalytic approaches to create promising fluorescent chemosensors and molecular probes for metal cations. Modification was carried out at atoms of the cryptand and at C atoms of the benzyl spacer. Macrotricycles and isomeric trismacrocycles were obtained via Pd-catalyzed macrocyclization reactions of, -bis(3,5-dibromobenzyl) diazacrown ether derivatives with oxadiamines using either BIAP or RuPhos ligands and were further modified with dansyl fluorophores. Acknowledgement: The work was financially supported by the RFBR grant [1] A.A. Yakushev,.M. Chernichenko, M.V. Anokhin, A.D. Averin, A.K. Buryak, F. Denat, I.P. Beletskaya. Molecules, 2014, 19,

133 P22 SYTHESIS F 1Н-IMIDAZLECARBXAMIDES I.V. Zavarzin, V.. Yarovenko, S.L. Semenov, E.I. Chernoburova, M.M. Krayushkin. D. Zelinsky Institute of rganic Chemistry, Laboratory for Chemistry of Steroid Compounds, Moscow, Russia We earlier proposed the method for synthesis of 4,5-dihydro-1Н-imidazolecarboxamides (1) by the reaction of chloroacetamides with aliphatic diamines in the presence of sulfur 1,2 (Scheme 1) R H Cl H 2 ( C H 2 ) n 2 H 2 R H Scheme 1 1 H ( C H 2 ) n n = 1,2 In this work we propose the method for the transformation of products 1 into 1Нimidazolecarboxamides 2. We found that the interaction of 1а-с with i/al alloy in aqueous methanol at 20 о С results in the dehydrogenation of dihydroimidazole fragments to form imidazoles 2а-с. R H H i/ Al, K H H M e H/ H 2 R 1 a -c 2 a -c R = 2 -F ; 3 - M e ; 2,4 -M e H Scheme 2 References 1. V.. Yarovenko, S.A. Kosarev, I.V. Zavarzin, M.M. Krayushkin, Russ. Chem. Bull. (Int. Ed.) 1999, o. 4, p M.M. Krayushkin, V.. Yarovenko, I.V. Zavarzin, Russ. Chem. Bull. (Int. Ed.) 2004, o. 3, p

134 P23 FEP/MD PRTCL T MDEL SELECTIVITY F KIASE IHIBITRS G.G. Chilov,.V. Stroganov, F.. ovikov, A.A. Zeifman, V.S. Stroylov, I.Yu Titov, I.V. Svitanko D Zelinsky Institute of rganic Chemistry RAS With over 500 different kinase enzymes encoded in a human genome and appreciation the role of kinases as promising therapeutic targets, the selectivity profile of a kinase inhibitor is an important indicator of its potential off-target effects including adverse effects, which sometimes might be quite severe and even preclude application of a drug in clinical practice. ne of the recent examples of how the lack of selectivity of a kinase inhibitor drug may restrict its clinical application because of abundant life-threatening adverse effects is presented by Ponatinib - a potent inhitor of Abl kinase (primary therapeutic target) as well as over 40 off-target kinases. With the intent to overcome adverse effcts of Ponatinib we designed a PF-114 molecule, which appeard to be comparable to Ponatinib with respect to Abl suppression, but inhibited only 10 off-target kinases. In order to rationalize enhanced selectivity we established a FEP/MD protocol in which for each kinase Ponatinib molecule was transformed to PF-114 and the dg of such transition was recorded. The modeled system consisted of a full atom kinase domain with inhibitor docked into ATP-bindin site and immersed in a box of explicit solvent. FEP transition was split into 3 steps: decharging initial molecule (Ponatinib), converting Van der Waals parameters to another molecule (PF-114) and then charging the resulting molecule. Each transition was split in its turn into 10 windows, each taking 2 ns of MD simulation. Totally 15 kinases were modeled for the selectivity of inhibition. It appeared that calculated selecivities correlaeted with experimental data with R of 0,63. Structural findings from FEP/MD simulations uncovered 2 factors contributing to the enhanced selectivity of PF-114: its unfavorable (compared to Ponatinib) interaction with main chain carbonyl oxygen present in the active site of BRAF, Src, ERBB4, FGFR1, VEGFR2, TRKC, TRKB; and unfavorable interaction with water molecule in the active sites of BRAF, EPHA7, FGFR1, FLT1, MAPK11, MAPK14 kinases. Current results suggests that full atomic FEP/MD modeling may be a valuable instrument in the design of kinase inhibitors with improved selectivity. 134

135 P24 FEATURES F ATURAL PLYSACCHARIDE BASED THI FILMS FRMATI Y.V. Chudinova 2, D.V. Kurek M.V.Lomonosov Moscow State University, Moscow, Russia 2 - Centre «Bioengineering», RAS, Moscow, Russia atural polysaccharide based thin films are promising biomaterials for using in different fields of science. Thin films were prepared by layer-by-layer (LbL) technique via alternately dipping the substrate into polycation and polyanion solutions to form polyelectrolyte multilayers. During each adsorption cycle one a monolayer is built up and the surface charge is reversed. This assembly process allows obtaining films with desired characteristic. Layer-by-layer method offers several advantages over other thin film deposition techniques, for example it is simple, rapid and inexpensive. Polyelectrolyte LbL films can be assembled from chitosan, pectin and other natural polymers. Pectin is one of the basic components of plant cell wall. It has a complex structure and contained linear and branched regions. Chitosan is produced by deacetylation of chitin, which is the structural element in the exoskeleton of crustaceans and cell walls of fungi. Chitosan and pectin are considered as some of the most attractive natural polyelectrolytes, because they are nontoxic, biodegradable, and biocompatible polymers. Their oppositely charged surface permits to use them for generating biocompatible surfaces via multilayer assembly. The main characteristic of biofilms, such as surface topography, roughness, thickness, molecular structure, adhesion forces were determined by atomic force microscopy (AFM). Influence of polyelectrolyte type and number of layers on the film buildup were investigated. Pectin covers mica surfaces very well and filling degree is nearly 100 %. Chitosan forms heterogeneous structures on the mica surface with a lesser filling degree. Chitosan with different molecular weight was studied. Results showed that in all cases were formed particles and aggregates. Influence of substrate type and its possible modifications was considered. Surface topography, height, roughness of the films which formed on the substrates with different properties were varied. Further, effect of the concentration and the presence of other polysaccharide were observed. Pectinchitosan and chitosan-pectin coatings which formed via layer-by-layer technique had different morphological characteristics. The adhesion of the polyelectrolyte multilayer films has been investigated by contact mode of AFM. Adhesion is the attraction forces between the AFM tip and the film surfaces by force-curves mode [1]. btained data demonstrated relationship between adhesion forces and surfaces properties. Understanding of the molecular structure and pathways of formation such thin films allows to predict the characteristics and produce coating materials for use in various fields of biology and medicine. References: 1. Guo Y.-B., Wang D.-G, Adhesion and friction of nanoparticles/polyelectrolyte multilayer films by AFM and micro-tribometer / Tribology International P

136 P25 SYTHESIS F -(PICRYLAMI)ITRPYRAZLES I.L. Dalinger, I.A. Vatsadze, T.K. Shkineva, A.V. Kormanov, S.A. Shevelev.D. Zelinsky Institute of rganic Chemistry Russian Academy of Sciences, Laboratory of itrogen-containing Aromatic Compounds, Moscow, Russian Federation ne of the directions of modern design of nitroazole-based high-energy compounds consists in the introduction of an -amino group to the endocyclic nitrogen atom of the nitroazole ring. This results in the preparation of -amino derivatives of nitrotetrazole [1], nitrotriazoles [1-3], nitroimidazoles [4], and nitropyrazoles [3, 5-8]. However, the possibility functionalization -aminonitroazoles additional energy-rich groups with saving of nitro groups in azole cycle poorly understood and limited only -nitration [4a], - trinitroethylation [3, 4c] and the introduction of a fragment of [1,2,4]triazolo[4,3-b]- [1,2,4,5]tetrazine [9]. In continuation of our works on chemistry of polynitropyrazoles [10] and for the purpose of broadening of synthetic potential of -aminonitroazoles as versatile building-blocks for constructing new energy-rich compounds we developed method functionalization -amino group using picryl fragment on the example of -aminonitropyrazoles 1. This method is based on arylation -aminonitropyrazoles 1 under the action of picrylchlorid (PicCl) in the presence of base (К 2 СО 3 ) when heated in MeC within 2-6 h. The result is synthesized representatives of a previously unknown type of energy-rich compounds - - (picrylamino)nitroazoles 2, which are isomers well known C-(picrylamino)nitroazoles [11]. Compounds 2 with two nitro groups in the pyrazole ring are organic H-acids medium strength (рка , in MeC-Н 2 О). [1] T.M. Klapötke, D.G. Piercey, J. Strierstorfer, Dalton Trans., 2012, 41, [2] P. Yin, Y. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2013, 1, 585. [3] Y. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2014, 2, 3200 [4] (a) R. Duddu., P.R. Dave, R. Domavarapy,. Gelber, D. Parrish, Tetrahedron Letters, 2010, 51, 399; (b) M.M. Breiner, D.E. Chavez, D.A. Parrish, Synlett, 2013, 24, 519; (c) P. Yin, Y. Zhang, Y. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2013, 1, [5] G. Hervé, C. Roussel, H. Graindorge, Angew. Chem., Int. Ed. Engl., 2010, 49, 3177 [6] C. He, J. Zhang, D.A. Parrish, J.M. Shreeve, J. Mater. Chem. A, 2013, 1, [7] V.M. Vinogradov, I.L. Dalinger, S.A. Shevelev, Mendeleev Commun., 1993, 111. [8] X. Zhao, C. Qi, L. Zhang, Y. Wang, S. Li, F. Zhao, S. Pang, Molecules, 2014, 19, 896. [7].V. Palysaeva, K.P. Kumpan, M.I. Struchkova, I.L. Dalinger, A.V. Kormanov,.S. Aleksandrova, V.M. Chernyshev, D.F. Pyreu, K.Yu. Suponitsky, A.B. Sheremetev, Оrg. Lett., 2014, 16, 406. [10] (a) I.L. Dalinger, I.A. Vatsadze, T.K. Shkineva, G.P. Popova, S.A. Shevelev, Synthesis, 2012, 44, 2058; (b) I.L. Dalinger, I.A. Vatsadze, T.K. Shkineva, G.P. Popova, S.A. Shevelev, Y.V. elyubina, J. Heterocycl. Chem., 2013, 59, 911. [11] (a) P.. euman, J. Heterocycl. Chem., 1970, 7, 1159; (b) M.D. Coburn, J. Heterocycl. Chem., 1970, 7, 345 and 1971, 8, 153. The research was supported by the Division of Chem. and Material Sciences of the RAS (Kh-4). 136

137 P26 MeLa X /Zr 2 CATALYSTS FR C XIDATI.A. Davshan, A.L. Kustov,.P. Tkachenko, L.M. Kustov IC RAS, Lab.14, Moscow, Russia Mixed metal oxides with a composition АВО 3 known as perovskites exhibit the high thermal stability and enhanced catalytic activity in C and hydrocarbon oxidation. The perovskite-type materials are less expensive as compared to supported noble metals. The materials can be significantly improved by supporting the perovskites onto porous carriers with a developed surface area. The goal of our work was to prepare, characterize and test in C oxidation a series of MeLa 3 perovskites (Me = Co, Fe, i) supported onto a mesoporous zirconia as a robust and durable carrier. The synthesis of mesoporous Zr 2 was carried out according to the previously developed and modified procedure [1]. A glycine complex of lanthanum and cobalt or iron or nickel was prepared by the recipe described in [2, 3]. The samples of supported lanthanum-metal perovskites were prepared by impregnation of the precalcined mesoporous carrier (Zr 2 ) with a solution of the prepared La-Co/Fe/i glycine complex. The chemical analysis of the samples for the contents of the metals (Zr, Co, i, Fe, and La) was carried out by atomic emission spectroscopy. Diffuse-reflectance FTIR spectra were recorded at room temperature in the frequency range of cm -1 with a resolution of 4 cm -1 using а ICLET Protege 460 spectrometer supplied with a diffuse-reflectance attachment. The following probe molecules were used to test surface sites of different nature: СО as a probe for Lewis acid sites and low-coordinated metal ions, CD 3 C as a probe for both Lewis and Broensted (if present) acid sites. The probe molecules were adsorbed at room temperature and equilibrium pressures of 5 Torr for СО, 96 Torr for CD 3 C (saturated pressures). The phase composition of the samples and the particle size of the supported metal were examined by X-ray diffraction (XRD) analysis. X-ray absorption (XAES + EXAFS) spectra (Co K edge at 7709 ev and i K edge at 8333 ev) were measured at the Hasylab X1 station (DESY,Germany) using a Si(111) double crystal monochromator. The EXAFS data analysis was performed using the software VIPER [4]. Reference spectra were taken using standard reference compounds: Co, Co 3 4, Co-foil, i, and i -foil. The required scattering amplitudes and phase shifts were calculated by the ab initio FEFF8.10 code [6]. X-ray photoelectron spectra were recorded by XSAM 800 spectrometer with Mg Kα X-ray ( ev) source. Catalyst testing was carried out in a laboratory scale fixed bed quartz reactor (internal diameter 3 mm), operating at an atmospheric pressure. The feed gas mixture consisted of 4.5 vol. % C, 22.5 vol. % 2 and He balance. The total feed flow rate was held constant at 10 cm 3 /min, with a volume hourly space velocity (VHSV) of 6000 h 1. The following order of the activity in C oxidation, as the temperature of the 50% conversion (T 50 ), was found in the temperature range from 50 to 400 C: LaCo 3 /Zr 2 (200 o C) > LaFe 3 /Zr 2 (275 o C) > Lai 3 /Zr 2 (300 o C). [1] V. A. Sadykov, L. A. Isupova, I. A. Zolotarskii, L.. Bobrova, A. S. oskov, V.. Parmon, E. A. Brushtein, T. V. Telyatnikova, V. I. Chernyshev, V. V. Lunin, Appl. Catal.A 204 (2000) 59. [2] E.V. Makshina, Thesis of Cand. Sci. Dissertation, Moscow State Univ., [3] L.M. Kustov, Top. Catal. 4 (1997) 131. [4] K.V. Klementiev, [5] A.L. Ankudinov, B. Ravel, J.J. Rehr, S.D. Conradson, Phys. Rev. B, 58 (1998)

138 P27 SELECTIVE FUCTIALIZATI F ALKYES WITH ATURALLY CCURRIG RGASULFUR CMPUDS E.S. Degtyareva, V.P. Ananikov Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia owadays crude oil remains one of the most important resources in the industry. Crude oil is a complex mixture mostly of hydrocarbons with small amounts of sulfur- and nitrogen-containing impurities. To produce more valuable fuels, oil fractions are subject to catalytic processes, like reforming, isomerization, and cracking. For ecological as well as technological reasons organosulfur components should be removed before the petroleum refining. However, it would be much more interesting to utilize these sulfur species as a naturally-occurring source of chemical reagents, for example for functionalization of hydrocarbons. The promising and efficient way to create a C-S bond is an addition reaction of thiols and disulfides to unsaturated hydrocarbons [1,2]. A convenient and selective metal-catalyzed methods for the addition of thiols and disulfides to alkynes have been recently reported. The present study is dedicated to the development of such catalytic system in order to involve crude oil as a reagent in organic synthesis. As the first step in our study we describe analytic approach for high sensitivity mass spectrometric measurements with ability to detect trace amount of products. Since most of the components in the crude oil are nonpolar, special polar tags were introduced for electrospray ionization (ESI) detection. To achieve this aim the alkynes with easily polarizable groups were synthesized. Good results were achieved using 1-(pentyn-4)-1H-imidazole, and in the model reaction involving the mixture of C 6 H 5 SH, C 6 H 11 SH and C 6 H 13 SH all products were clearly detected (Figure 1). Detailed study of the catalytic system and ESI-MS characterization will be presented and discussed. Figure 1. An example of ESI spectrum registered for the reaction mixture in the crude oil. (1) Ananikov, V. P.; Kabeshov, M. A.; Beletskaya, I. P.; Khrustalev, V..; Antipin, M. Y. rganometallics 2005, 24, (2) Ananikov, V. P.; rlov,. V; Zalesskiy, S. S.; Beletskaya, I. P.; Khrustalev, V..; Morokuma, K.; Musaev, D. G. J. Am. Chem. Soc. 2012, 134,

139 P28 PLATIUM GRUP METALS CMPLEXES F HYBRID CHALCGE LIGADS: SYTHESES, STRUCTURES AD CATALYSTS I C-C CUPLIG REACTIS S. Dey Chemistry Division, Bhabha Atomic Research Centre, Mumbai , India The chemistry of chalcogenated platinum group metal complexes has been of considerable interest for several years due to their fascinating structural features, their relevance in catalysis [1] and lately in materials science [2,3]. These complexes are mostly non-volatile, insoluble or poorly soluble oligomeric species in organic solvents, thus limiting their utility as precursors for the synthesis of metal chacogenides for electronic devices or making them inconvenient for any homogeneous catalysis reaction. To inhibit polymerization of metal chalcogenolates and to develop phosphine free Pd-catalysts, internally functionalized ligands, containing both soft chalcogen and hard donor atoms has been quite successful, such as pyridine chalcogenolates [4] or aliphatic amine chalcogenolate ligands [5,6]. We have designed and developed several internally functionalized ligands ( E) 2, EAr (E = S, Se, Te; E = Me 2 CH 2 CH 2 E, Me 2 CH 2 CH 2 CH 2 E; Ar = Ph, tol, Mes) and bis(4- pyridyl)dichalcogenide and synthesized their palladium(ii) and platinum(ii) complexes. Versatile coordination behaviour of these ligands are shown in their complexes (Chart 1). The unusual colour of [MCl(E )(PR 3 )] (blue-violet: Pd, red: Pt) has been attributed due to metal mediated ligand (E) to ligand (PR 3 ) charge transfer transitions. The cationic complexes [Pt(PEt 3 ) 2 (py 2 E 2 )] 2 (CF 3 S 3 ) 4 with Pt pyridyl bond have been isolated via self-assembly reaction. The complexes [PdCl 2 ( EAr)] n exist in monomer and dimer forms, their ratio depends on the size of chelate ring and chalcogen atom. The catalytic activity of [PdX( E)] n (X = Cl, Ac), [PdCl 2 ( EAr)] n and trans-[pdcl(4-sepy)(pph 3 ) 2 ] in Suzuki C C cross coupling reaction will also be discussed. Chart E M E M M E X M E E M X Ar X E M X X M E X Ar M E E E E M +4 E M M E E M Acknowledgement: Dilip Paluru, K. V. Vivekananda, A. Wadawale,. Bhuvanesh, B. M. Bhanage and V. K. Jain are acknowledged for collaborations. References 1. Q. Yao, E. P. Kinney, C. Zheng, rg. Lett. 2004, 6, S. Dey, V. K. Jain, Platinum Met. Rev. 2004, 48, B. Radha, G. U. Kulkarni, Adv. Funct. Mater. 2010, 20, K. V. Vivekananda, S. Dey, A. Wadawale,. Bhuvanesh, V. K. Jain, Dalton Trans., 2013, 42, D. K. Paluru, S. Dey, A. Wadawale, V. K. Jain, J. rganomet. Chem. 2013, 728, B. J. Khairnar, S. Dey, V. K. Jain, B. M. Bhanage, Tetrahedron Lett. 2014, 55,

140 P29 THE REACTIS F 1,3-DIARYL-3-CYCLHEXAILPRPAE-1- E WITH HYDRGE SELEIDE I SITU I CDITIS F ACID CATALYSIS D.Yu. Direnko 1, Ya.B. Drevko 2, B.I. Drevko Penza branch of the military Academy of logistics 2 - FGU VP Saratov State Agrarian University named after.i. Vavilov It is known that when arylaliphatic 1,5-dicetones interacts with hydrogen selenide in conditions of acid catalysis the corresponding 4H-selenopyran structures can be formed 1, which are used as veterinary and healthcare products. However, dicyclic diaryl-4h-selenopyrans have not been described until today. We have studied the chemical reaction of 1-paramethoxy-3-phenyl-3-cyclohexanonilpropane-1-one 1 with hydrogen selenide in situ in conditions of acid catalysis. The reaction has been conducted in the presence trimethoxyphosphine 1. In the result of the compound 1 was obtained in 2- paramethoxy-4-phenyl-5,6,7,8-tetrahydro-4h-selenochromen 2 with quantitative output 80% (Melting point = С). Ph Ph C H 3 H P C l 3 Z n S e Ph - C H p Se Ph 3 - C H p In the course of reaction settled crystal compounds and mother solution were analyzed by method of the capillary gas-liquid partition chromatography with mass-selective detector HP 5890/5972: T inj =200 о С, t set =3 min; T set =50 о С; T end =280 о С; Т = 10 о С/min; carrier gas helium, = 1 ml/min. It was found that every molecular ion or fragment which contained selenium presented in the form of six signal intensities conforming to the content of the selenium isotopes in the nature: Se 74 (0,87%), Se 76 (9,02%), Se 77 (7,58%), Se 78 (23,52%), Se 80 (49,82%), Se 82 (9,19%). The compound 2 is subjected to isomerisation at high temperature. So, there are signals of four compounds with retention time 27,03 min, 29,06 min, 29,3 min, 40,08 min on the chromatogram (m/z = 381, the output of this molecular ion is accompanied by loss of one hydrogen s isotope). As well as, one compound was identified and its molecular ion was conformed to dehydroselenochromen (m/z = 380, retention time is 33,35 min). This ion also was identified through GH-MS that confirmed the received mass spectrum. Therefore formation of product (dehydroselenochromen (m/z = 380)) demonstrates the new direction of disproportionation of dehydroselenochromen structures on alicyclic fragment. Literature 1. Drevko Ya.B., Fedotova.V. The synthesis of the first representatives of benzenediamine dehydroselenochromens // CHC P

141 P30 SYTHESIS F UATURAL PRLIE DERIVATIVES USIG THE AZA- CPE-MAICH-REACTI D.S. Belov,.K. Ratmanova, A.V. Kurkin, I.A. Andreev Lomonosov Moscow State University xygenated bicyclic amino acids constitute an important class of secondary metabolites. Many of these nonproteinogenic amino acids are subunits of structurally diverse natural products. Various methods to access these biologically important compounds were advised by synthetic community and subsequently used by pharmaceutical companies. However pharmaceutical industry usually relies on the most robust and reliable reactions. Aza-Cope-Mannich rearrangement is a powerful reaction which was successfully used in academia settings, was however largely overlooked by medicinal chemists. 1 We have shown recently that it can be routinely scaled up to 1 mole. 2,3 In this work we demonstrated that a number of proline analogs can be efficiently prepared with full control of stereochemistry. Scheme 1. The aminoalcohols required for the rearrangement were effectively prepared in several steps form commercially available oxiranes (Scheme 1). The aza-cope-mannich reaction provided both cis and trans fused unnatural proline analogs 2, 3 or 4 in high yields. The ratio of products was dependent upon the reaction conditions and the nature of substituents R 1 and R 2. The reaction also proved to be scalable (>1 g). This study was supported by the Russian Foundation for Basic Research. (Projects o , , ). 1. verman, L. E.; Humphreys, P. G.; Welmaker, G. S. rg. React. 2011, 75, Belov, D. S.; Lukyanenko, E. R.; Kurkin, A. V.; Yurovskaya, M. A. Tetrahedron 2011, 67, Belov, D. S.; Lukyanenko, E. R.; Kurkin, A. V.; Yurovskaya, M. A. J. rg. Chem. 2012, 77,

142 P31 SYTHESIS F XYGEATES F DIFFERET CLASSES HETERGEIUS KCMS-CATALYSTS V.S. Dorokhov,.L. Eliseev, A.L. Lapidus, V.M. Kogan. D. Zelinsky institute of organic chemistry, Moscow, Russia Heterogeneous catalytic systems based on alkali-modified molybdenum disulphide are promising for alcohols synthesis from СО and Н 2 [1,2]. The model of dynamic nature of the active sites of transition metal sulphide catalysts was taken as a conceptual basis for the work [3]. We conducted investigations of structure and functioning mechanism of MoS 2 -based catalysts active phase in oxygenates synthesis reaction. We found out that alkali metal (potassium) forms unite phase with MoS 2 and significantly changes it structure. Addition of potassium increases average number of layers and average linear size of MoS 2 crystallites. As it follows from our catalytic experiments, both Co and K increases selectivity of alcohols formation. Besides addition of potassium suppresses hydrogenation and hydrodesulphurisation reactions [4]. We suggested that formation of alcohols from СО and Н 2 occurs on active sites located on the "edges" of the MoS 2 slabs. It is likely that active sites responsible for alcohols synthesis consist of a combination of two MoS 2 clusters, one of which is promoted with Co, and K is intercalated between the crystallite layers. Formation of alcohol molecule depends on accessibility of alkali ion to coordination of alcoxyl intermediate oxygen. The scheme of possible mechanism of synthesisgas conversion on KCoMoS catalyst was published in [5]. The addition of ethanol or ethylene to synthesis gas substantially changes the reaction rate and composition of the products [5]. Presence of these components in the gas feed can significantly increase C conversion. According to our results alcohols can adsorb on KCoMoS-catalysts active sites and enter a series of side reactions, which leads to formation of ethers, esters, aldehydes, ketones and organic acids. Therefore, the use of additives to syngas makes it possible to obtain a wide range of oxygenates of different classes. The further development of this approach can be efficient for controlling selectivity in processes of simultaneous synthesis of various classes of organic compounds. Acknowledgment. This work was financially supported by the Russian Foundation for Basic Research (Project o mol_a). References: 1) Surisetty V.R. et al. App. Cat. A 404 (2011) ) Feng M. Recent Patents Catal. 1 (2012) ) Kogan V.M., ikulshin P.A., Rozhdestvenskaya.. Fuel 100 (2012) ) Dorokhov V.S. et al. Kinetics and Catalysis 54 2 (2013) ) Kogan V.M. et al. Russ. Chem. Bull. 2 (2014) in press. 142

143 e ffe c t o f K, C o a n d s u p p o rt H P32 THE MECHAISM F ALCHL FRMATI VER TMS CATALYSTS V.S. Dorokhov 1, E.A. Permyakov 1,.L. Eliseev 2, V.M. Kogan D. Zelinsky Institute of rganic Chemistry, RAS, Laboratory of catalysis by trasition metals and their compounds, Moscow, Russia 2 -.D. Zelinsky Institute of rganic Chemistry, RAS, Laboratory of catalytic reaction of carbon oxides, Moscow, Russia The aim of this work is to investigate a structure of transitional metal sulfide (TMS) catalyst active sites in mixed alcohol synthesis (MAS) from synthesis gas and to develop possible mechanism of this reaction. The model of dynamic nature of the active sites of TMS catalysts was taken as a conceptual basis for the work [1,2]. As it follows from our catalytic experiments, both Co and K affect alcohol selectivity towards hydrocarbon (HC) formation. It is likely that the active sites responsible for alcohol formation are located on the "edges" of the MoS 2 slabs. Besides, K poisons C-S hydrogenolysis sites and HDS activity decreases. Basing on the experimental data, we suggest the structure of the MAS site as a combination of two MoS 2 clusters, one of which is promoted with Co, and K is intercalated between the crystallite layers and the scheme of possible mechanism of synthesis-gas conversion on K-Co-Mo-S catalysts (Fig. 1). S S Co Mo H 2 C S C n H 2n+1 Mo S H Mo K S H Co S C n+1 H 2n+3 H C n+1 H 2n+4 C n H 2n+1 Mo S S S Co Mo S K S Mo Mo CH 3 H Co Mo H C H S S 3 Mo Mo K S S S S S S C S S Co Mo H 143 C S Co K H H S Mo Mo S S Mo 2H H S S H Co Mo Co e ffe c t o f K, C o and support H S C H 2 S C S S C H H 2 Mo Fig. 1: Suggested Mo Mo Mo Mo K Mo K K mechanism of S S S S S S S S S S S S 3H alcohols and HC H 2 formation over H H 2 H H 3H C H H 4 3 KCoMoS active C C Mo Co H Mo n H 2n+1 Mo Co Co Mo Co C n-1 H 2n-2 H sites. Black S S nc C H S S C S S C S 2H S C 3 rectangle defines Mo Mo Mo Mo Mo Mo Mo Mo K K K K the initial step of S S S S S (4 n -4 )H S S S S S S S S S S S (n -1 )H 2 reaction. As an initial step of the mechanism, C adsorption on the vacancy was taken. After partial hydrogenation of carbon by dissociatively adsorbed hydrogen, the C= bond lengthens allowing the oxygen atom to coordinate on K + ion intercalated between the MoS 2 crystallite layers. Coordination of the oxygen on the K + ion stabilizes the alkoxylenated intermediate and prevents the C- bond from breaking, which is necessary for the succeeding process of alcohol formation. xygen coordination onto the Mo atom of the neighboring cluster leads to hydrogenolysis of the C- bond. The alkyl fragment can either be hydrogenated to form HC or take part in the carbon-chain growth next C molecule is inserted between C and Mo. xygen of a newly inserted C can coordinate on K or Mo determining formation of either alcohols or HC. It was found that the ratio of alcohols to HC yields decreases with an increase of reaction temperature. It means that alcohols formation becomes kinetically less favorable at higher temperatures than the C- bond hydrogenolysis. This observation is in agreement with the suggested mechanism. [1] V.M. Kogan, P.A. ikulshin,.. Rozhdestvenskaya, Fuel 100 (2012) [2] V.M. Kogan, P.A. ikulshin, Catal. Today 149 (2010) C S H K S Mo Mo Mo S S S

144 P33 CATALYTIC CYCLMAGESIATI F 1,2-DIEES I THE SYTHESIS F PHERMES AD ACETGEIE S PRECURSRS V.A. Dyakonov, A.A. Makarov,.A. Trapeznikova, U.M. Dzhemilev Institute of Petrochemistry and Catalysis, Russian Academy of Sciences; Laboratory Catalytic Synthesys; Ufa; Russia An efficient method for the synthesis of valuable -, О-, and Si-containing 1Z,5Z-diene compounds was developed. The method comprises Cp 2 TiCl 2 -catalyzed cross-cyclomagnesiation of 1,2-dienes by Grignard reagents (RMgR ) to give 2,5-dialkylidenemagnesacyclopentanes in up to 96% yields. This approach was successfully used in the synthesis of 5Z,9Z-dienoic acids, precursors of acetogenins and insect pheromones Q R () n [T i], M g E tm g B r Q H R 3 + (D 3 + ) () n Q () n Mg 3 4 [T i] = C p 2 T ic l 2 ; n = 1, Q = T M S : R = B n (k ), H ex (l); n = 2 : Q = B n, R = H ex ( a ); Q = T H P, R = H ex (b ); Q = T H P, R = B n (c); Q = M o rp h, R = B n ( h ); Q = M o rp h, R = H ex ( i) n = 3 : Q = T H P, R = C 12 H 25 (d ); n = 4 : Q = T H P, R = B u (e); Q = T H P, R = H ex (f); n = 6 : Q = T H P, R = B u ( g ). Acylation of diene 4g with acetyl bromide gave hexadeca-7z,11z-dien-1-yl acetate 5, the pink bollworm Pectinophora gossypiella attractant, in a final yield of 89%.. E tm g B r [T i], M g T H P -( C H 2 ) T H P -( C H 6 2 ) H 6 ( C H 2 ) 3 M e ( C H. 2 ) 3 M e Mg 94% 3g M e ( C H 2 ) 3 M e Br ( C H 2 ) 3 M e T H P -( C H 2 ) 6 A c -( C H 2 ) 6 89% 4g 5 The same approach was used to obtain the key synthons in the preparation of some acetogenins exhibiting high antitumor, antimalarial, and immunosuppressive activities. Cross cyclomagnesiation of 1,2-hexadecane and 2-(4,5-hexadiene-1-yloxy)tetrahydropyran followed by hydrolysis furnished 2-(hexacosa-4Z,8Z-dien-1-yloxy)tetrahydropyran 4h (yield 84%), which is the key intermediate in the preparation of the acetogenin cis-solamin 6. R T H P ( ) 10 + ( ) 2.. E tm g B r, [T i] 20 o C, E t 2 ( ) 10 ( ) 2 Mg 3h T H P H % ( ) ( ) H 2 3 C 10 2 T H P 1 2 ( ) 11 H H 4h H H 6 This work was performed under financial support from the Russian Science Fondation (Grant ) and by Russian Foundation for Basic Research (Grant ) 144

145 P34 SYTHESIS AD ATIHELMITIC ACTIVITY F 5--DERIVATIVES F IVERMECTI I.V. Zavarzin 1, M.Kh. Dzhafarov 2,.V. Krukovskaya D. Zelinsky Institute of rganic Chemistry, RAS, Moscow, Russia 2 - K.I. Skryabin Moscow State Academy of Veterinary Medicine and Biotechnology, Moscow, Russia Ivermectin 1 and its derivatives are widely used as antihelmintic medical formulations. In this case, the parasites eventually develop resistance to these substances. 1,2 It is therefore highly relevant to develop new antihelmintic agents. We were the first who obtained the 5--ivermectin derivatives 2 by acylation of an ivermectin 1 anhydrides of carboxylic acids. In addition to the carboxylic acids the corresponding esters and amides are also obtained. R C H 3 C H 3 H M e C H 3 C H 3 C H 3 C H 3 M e H 1 : R = M e, E t R 1 = H 2 : R = M e, E t R1 C H 3 R 1 = H Carboxylic acid 2, as well as their esters and amides show high antihelmintic activity. Literature: 1. Tyrell К., Leo F., Veterinary Parasitology Р Varady M., Cobra J., Letkova V., Kovac G., Veterinary Parasitology Р

146 P35 TREDS I EVLUTI F ATIPARASITIC CHEMICAL AGETS M.Kh Dzhafarov K.I. Skryabin Moscow State Academy of Veterinary Medicine and biotechnology Chemotherapy and prevention are of high priority in control of helminthoses and other dangerous parasitoses of humans, animals and plants [1]. However, the intensive administration of antiparasitic preparations leads to development of resistance, which is one of the ways of biochemical adaptation of helminths, insects and arthopods to the first- and second-order environmental changes (the host and ecological niche occupied by the host, where certain stages of the complex-cycle pest metamorphoses take place), which necessitates regular renewal of the range of chemical agents, among different measures [2]. Systematization of the data on the antiparasitic substances in the light of new discoveries and developments is an important step for a successful struggle against parasitic diseases. In particular, based on the systemic analysis of features of the chemical structure of anthelminthic substances, the hypothesis on the viability of the targeted search for such compounds among the derivatives of conditionally progenitor cyclic hydrocarbons benzene, indene, naphthalene, 1Нcyclopenth [a]-naphthalene, anthracene and phenanthrene by alternating absolutely unsaturated and saturated structures, including heterocyclic analogues containing nitrogen, oxygen and sulfur and different substitutes and functional groups, was voiced: References 1. Dzhafarov M.Kh. Russian J. Agrobiology. Animal biology series. 2013, 4, p Dzhafarov M.Kh., Vasilevich F.I. Advances in Pharmacology and Pharmacy. 2014, 2:

147 P36 RHDIUM-CATALYZED REDUCTIVE CARBYLATI F IDBEZEE.L. Eliseev, T.. Bondarenko, T.. Myshenkova, A.L. Lapidus.D.Zelinsky Institute of organic chamistry, Moscow, Russia Aromatic aldehydes is useful class of products because of diverse reactivity of formyl group. Usually they are synthesized by Gattermann Koch, Reimer Tiemann, Vielsmeier Haag, and Duff reactions. However, these methods suffers from drawbacks like low yield, poor selectivity and generating waste and side products. 1,2 Alternatively, catalytic formylation (reductive carbonylation) of aryl halides with synthesis gas in the presence of palladium phosphine complexes was firhst reported in 1974 by Schoenberg and Heck 3 and lately by Beller 4 6 and agarkar 7 groups. Somewhat surprisingly, up to now rhodium was unexplored as a catalyst for reductive carbonylation of aryl halides. This encouraged us to test rhodium salts and complexes in reductive carbonylation of iodobenzene as a model substrate. I + C + H 2 R h -cat. b ase C H + b aseh I Rhodium phosphine complexes such as HRh(C)(PPh 3 ) 3 and RhCl(C)(PPh 3 ) 2 were found to be excellent catalysts They surpass PdCl 2 (PPh 3 ) 2 in respect to activity and selectivity to benzaldehyde. Aromatic solvents such as toluene and o-xylene seems to be the most suitable medium ther solvents such as heptane, 1,4-dioxane, MEK, DMF and acetonitrile gave poor yield of benzaldehyde. In methanol solution, methyl benzoate was the main product. Reaction is highly sensitive to the nature of the base. Replacing Et 3 with Bu 3 resulted in almost threefold reduction in benzaldehyde yield. Somewhat higher but still low yield was achieved with Hünig's base. Inorganic bases such as potassium and cesium carbonates gave poor iodobenzene conversion and benzaldehyde yield. Synthesis gas pressure renders effect on reaction. Iodobenzene conversion reaches 100% at a total pressure of about MPa and slightly decreases at higher pressure. Both selectivity and yield of benzaldehyde increase with pressure increasing while selectivity to benzene decreased. Biphenyl is a main product at atmospheric pressure but it fully disappears at a pressure 1 MPa and higher. In conclusion, rhodium (I) triphenylphosphine complexes are good catalysts for reductive carbonylation of iodobenzene. The best catalyst formulation found: 0.5% RhCl(C)(PPh 3 ) 2, 150% Et 3, toluene. At 110 C and 1.5 MPa (C/H 2 = 1/1) iodobenzene is totally converted within 2 hours giving benzaldehyde with the yield of 88%. References 1. F. Aldabbagh, Compr. rg. Funct. Group Transform. II, 2005, 3, L. P. Crawford, S. K. Richardson, Gen. Synth. Methods, 1994, 16, A. Schoenberg, R. F. Heck, J. Am. Chem. Soc., 1974, 96, S. Klaus, H. eumann, A. Zapf, D. Sturbing, S. Hubner, J. Almena, T. Riermeier, P. Groß, M. Sarich, W.-R. Krahnert, K. Rossen, M. Beller, Angew. Chem. Int. Ed., 2006, 45, A. Brennfuhrer, H. eumann, St. Klaus, T. Riermeier, J. Almenab, M. Beller, Tetrahedron, 2007, 63, H. eumann, R. Kadyrov, Xiao-Feng Wu, M. Beller, Chem. Asian J., 2012, 7, A. S. Singh, B. M. Bhanage, J. M. agarkar, Tetrahedron Letters, 2011, 52,

148 P37 MDELIG F THE ELECTRCHEMICAL IMPEDACE I ADIC DISSLUTI F IR USIG A GEETIC ALGRITHM APPRACH A.R. Enikeev 1, I.M. Gubaidullin 2, M.A. Maleeva Institute of petrochemistry and catalysis, Laboratory of mathematical chemistry, Ufa, Russia 2 - Institute of petrochemistry and catalysis Laboratory of mathematical chemistry 3 - A.. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia In order to predict the general corrosion damage to metals and alloys, development of deterministic models and the acquisition of values for various model parameters are of paramount importance. ow it is generally accepted that elucidating an intricate reaction mechanism by means of steadystate techniques alone is a very difficult task [1]. In fact, the steady-state approach provides too little information in comparison with the complexity of the process under investigation. In the present work, we used model with three adsorbed species it was possible to explain the iron dissolution in sulphate and chloride media. It was recently found that impedance diagrams reveal at least three time constants concerning the faradaic process in the iron-sulphate systems was proposed by Keddam [2]. Reaction mechanis. The reaction kinetic parameters was calculated by genetic algorithm. The experimental impedance diagrams showed one high-frequency capacitive arc and three time constant at lower frequencies appearing as inductive or capacitive loops. They are attributed in the models, respectively, to the double layer capacitance in parallel with the transfer resistance and to the relaxation of three reaction intermediates. 1. E J Kelly, J Electrochem Sot 112, M Keddam, R Mattos and H Takenoutl, J Electro-them Sot 128, 257, 266 (1981). 148

149 P38 KIETICS AD MECHAISM F THE CATALYTIC XIDATI F 4- TERT-BUTYLPHEL BY AQUEUS SLUTIS F H 2 2 I THE PRESECE F TITASILICATES L.V. Enikeeva, I.M. Gubaydullin,.F. Murzasheva Institute of petrochemistry and catalysis RAS, Laboratory of mathematical chemistry, Ufa, Russia Selective oxidation of phenol is of great interest in terms of education practically valuable product - hydroquinone and catechol. This work is part of studies on the oxidation of phenols in aqueous solutions of hydrogen peroxide in the presence of metallosilicates. For initial evaluation of the activity of titanosilicate catalysts in oxidation reactions of organic compounds, we used a decomposition reaction of H 2 2 in the absence of substrate. We studied the catalytic activity in the decomposition reaction metallosilicates H 2 2 : apparent activation energy of the reaction in the presence of different samples metallosilicates were calculated; expression for the reaction rate, which shows good agreement with the experimental data, was proposed; model validation on the value is performed. A series of catalytic activity of the samples in the reaction of hydrogen peroxide decomposition was created. At the moment we study the oxidation reaction of tretbutilfenola by aqueous solutions of H 2 2. The scheme of the reaction, the reaction kinetic parameters was calculated. 149

150 P39 EW CHEMICAL TRASFRMATIS F i(acac) 2 WITH PSSIBLE IVLVEMET F SUPERATMIC i 2 2 CRE AS REVEALED BY ESI- MS AD MS/MS D.B. Eremin, V.P. Ananikov Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia More than twenty signals of nickel-containing ions were detected upon studying of electrospray ionization mass spectrum of the i(acac) 2 sample prepared in a plastic tube. However, changing sample preparation procedure to a glass vial gave a clear spectrum with four signals corresponding to: m/z , [i(acac) 2 + a] + ; m/z , [i 2 (acac) 3 ] + ; m/z [i 2 (acac) 4 + a] + ; and m/z , [i 3 (acac) 5 ] + (Figure 1A). A prominent difference in the spectra was caused by various plastic-derived contaminants, that were coordinated to the metal center. Figure 1. (A) ESI-MS spectra of solution of i(acac) 2 in acetonitrile prepared under standard conditions (with contaminant signals marked by blue symbols) and prepared without a contact with plastic (m/z = range; acac = C 5 H 7 2 ); (B) Experimental survival yield curves of most abundant ions. CID (Collision-induced dissociation) MS/MS experiments were carried out to estimate relative stability and to study reactivity during fragmentation process. Fragmentation of the bimetallic ion [i 2 (acac) 3 ] + was of most interest. Eight fragment ions of different composition were detected. Seven of them were formed as a result of C C, C H and C bond cleavage; nevertheless, they retained the i 2 2 core, a supposed superatomic structure, which caused exceptional behavior observed in the fragmentation. After the fragmentation at the applied collision energy of 40 ev, ketene, pentyn-3-on-2, buten-3-on-2, acetaldehyde, carbon monoxide, and hydroxide-anion were formed. ther bi-, tri- and monometallic species detected did not undergo such transformations under MS/MS conditions. Survival yields were calculated (Figure 1B), and a series of relative stability was proposed: i 2 >> i 1 i 3. The signal of [i 2 (acac) 3 ] + remained as most intensive after heating of the solution. Mass spectra with the similar ionic composition were obtained for vanadyl and copper(ii) acetylacetonates as well as after the addition of two-fold excess of acetylacetone to the solution of the acetates M(Ac) 2 (M = i, Cu, Pd). Chemical reactivity of detected ions and the role of bimetallic species are currently under investigation. 150

151 P40 FRMATI F A CMPLEX WITH FLURGEE LABEL IS A RELIABLE WAY F CREATI F A EXPRESS-METHD F ACETYLCHLIESTERASE ACTIVITY ASSAY.V. Fateenkova, E.T. Gainulina, D.K. Gulikova, S.B. Ryzhikov, V.. Fateenkov I.M. Sechenov First Moscow State Medical University, Faculty of Pharmacy, Russia, Moscow Assay of erythrocyte acetylcholinesterase (AChE) activity of human is widely used for the successful decision of many problems facing to a modern science: development of effective antidots for treatment of defeats by toxic organophosphorus inhibitors, medicines for treatment of illness Alzheimer and Parkinson etc. In a lot of cases there is a necessity of express-analyses of defeat by toxic organophosphorus inhibitors. As an example it is possible to refer to events in the Tokyo underground in 1985 year and also in territory of several syrian cities in 2013 year, when in the terrorist purposes sarin has been applied and there was a necessity of urgent diagnostics of a degree of defeat of significant number of victims of this act of terrorism. Known methods of AChE activity assay do not correspond to modern requirements to correlation of parameters sensibility - time of formation of an analytical signal». In the given work the express-method of acetylcholinesterase activity assay is offered on the basis of formation of an intensively fluorescing complex by the given enzyme with fluorogene label thioflavine T (TF). TF is reversible inhibitor of AChE and selectively binds to the peripheral site of this enzyme. Figure. Dependence of fluorescence intensity of TF (15 М) from AChE activity. With increase of AChE activity at constant concentration of ТF (15 М) in the investigated interval of reagents concentrations the dependence of fluorescence intensity of system TF - AChE has linear character (fig.). At addition AChE to solution TF formation of an analytical signal (increase of fluorescence intensity) on a wave of 490 nm is observed within of several seconds, and the achieved of fluorescence intensity remains stable more than 15 min. The absence of influence of human butirylcholinesterase and bull whey albumin on fluorescence intensity of thioflavine T on length of a wave of 490 nm is confirms selective character of interaction of human erythrocyte acetylcholinesterase with TF. 1. De Ferrari G.V., Mallender W.D., Inestrosa.C., Rosenberry T.L. J. Biol. Chem , Antokhin A.M., Gainullina E.T., Taranchenko V.F., Ryzhikov S.B., Yavaeva D.K. Russ. Chem. Rev ,

152 P41 QUATUM CHEMICAL MDELIG F CFRMATIS F TERT- BUTYL HYDRPERXIDE G.T. Garaeva, V.I. Anisimova, I.A. Suvorova,.. Batyrshin Kazan ational Research Technological University, , Kazan, K.Marks 68 Data on internal rotation of tert-butyl hydroperoxide (TBHP) advance the field of conformational analysis and can be used for investigation of reactivity of industrially important hydroperoxides which are primary products of hydrocarbon oxidation processes. For TBHP, internal rotation only about C- and - bonds is possible. Earlier it was demosntrated that TBHP has two conformations gauche and trans [1]. Figure 1 (curves 1,2) shows that all possible equilibrium structures of TBHP have identical energy, while analysis of bond lengths and angles (Table 1) also supports identity of these structures, and, therefore, monomeric form of TBHP exsists only in one conformation (Fig. 2) [2]. Table 1 Parameters of TBHP according to B3LYP/ G(df,p) calculations. Bond length, Å Angle, Torsion angle, H, С-О О-О О-Н СОО ООН С 2 С 1 О 1 О 2 С 3 С 1 О 1 О 2 С 4 С 1 О 1 О 2 С 1 ООН sm Fig. 1 PES of internal rotation of BHP: 1- around О-О bond, 2 around С-О bond Fig. 2 Molecule of TBHP 1 Suvorov, I. A Association and the thermal decomposition of tertiary hydroperoxides: Thesis Candidate. chem. sci./i.a. Suvorov. - Kazan, p. 2 Anisimov, V.I. Quantum-chemical study of the hydrogen bonds between molecules tertiary butyl hydroperoxide // V.I. Anisimova, I.A. Suvorov,.. Batirshin, V.I. Sokolov, K.E. Kharlampidi // Vestnik Bashkir University v (1). - p The work was supported by Russian Ministry of Education and Science within the framework of basic part (PIL 02.14). 152

153 P42 SUPRAMLECULAR ITERACTI F CAFFEIE MLECULES WITH EACH THER, WATER MLECULES AD XYGE ATMS F TETRAXIDAIS I THE EW CMPUD CBALT HEXAHYDRATE DIPERRHEATE CAFFEIE K.E. German 1, M.S. Grigoriev 1, G.V. Kolesnikov 2, Yu.A. Ustynyuk 2,.I. Slyusar 3, Ya.A. bruchnikova 3,.S. Kryzhovets 3, M.. Glazkova A.. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia; Medical Institute REAVIZ, Moscow, Russia 2 - Lomonosov Moscow State University, Moscow, Russia 3 - Medical Institute REAVIZ, Moscow, Russia Recently the antitumor and radiosensitizing drugs being caffeine derivatives that penetrate easily through blood brain barrier have been developed. They are effective with radiation and chemotherapy treatment for cases of brain tumors. Results of these studies has shown the caffeine derivatives as perspective source for receiving therapeutic agents to be used in a combined therapy for primary and metastatic brain tumors. Anyhow the mechanism of caffeine interaction was not clear. To provide the proper understanding of caffeine action the precise structural data are necessary. To increase the accuracy of the structural date and to simulate the interaction of caffeine with tetraoxidoanion and hydration water molecules the synthesis of caffeine cobalt hexahydrate perrhenate was carried out from saturated water solutions and the single crystal thus obtained were subjected to X-ray structural study at Bruker KAPPA APEX II diffractometer. Supramolecular interactions of caffeine molecules with each other, water molecules and oxygen atoms of tetraoxidoanions as in a new compound of Co(H 2 ) 6 [Re 4 ] 2. caffeine are analyzed in these study through comparison of the new precise structural data with quantum chemical analyses. The reasons for alterable orientation of caffeine molecules to each other and for the H-bonds network formation has been evaluated. 1. Vartanyan L.P., Kolesova M.B., Gornaeva G.F., Pustovalov Yu.I. Caffeine derivatives perspective method of the search for anticancer and radiomodifying drugs in combined therapy for malignant brain tumors // Psychopharmacol. Biol. arcol Vol. 5, 4. P Central Research Institute of Roentgenology and Radiology, Saint Petersburg 153

154 P43 EFFICIET CVERSI F ALKEYES T 2- METHYLEEDIHYDRPYRRLES P.R. Golubev, A.S. Pankova St. Petersburg State University, Institute of chemistry, St. Petersburg, Russia Earlier we have developed a method for the synthesis of cross-conjugated ketones 2 and investigated their interaction with common binucleophiles hydrazines and amidines [1,2]. ur next goal was to study the reaction of enynones 2 with amines. It was shown earlier [1,2] that the ethoxymethylene group is the most active center of ketones 2 in reactions with nucleophiles. In line with this, enamines 3 were obtained on the first stage in reactions with amines. Various solvents were used successfully in this reaction, but diphenyl ether was considered to be the most convenient, since in this case both synthetic steps could be performed in a one-pot fashion without isolation of intermediate enamines 3. We proposed that thermolysis of enamines 3 could lead to their cyclization via Michael-type intramolecular addition of amine nitrogen atom to a triple bond. We have found that this reaction proceeds smoothly at 200 C as a 5-exo-dig cyclization leading to pyrrolinones 4 as single products in good to excellent yields. Various amines with alkyl, aryl or heteroaryl substituents were used. Thus, monoalkylamines are predictably the most active coupling partners, but in this case steric factors play a crucial role. evertheless, even tert-butylamine was employed successfully in this reaction along with n-alkyl- and (hetero)benzylamines. In case of anilines the reaction outcome was fully consistent with nucleophilicity of the amine used. Generally, anilines with electron-donating substituents reacted more readily and provided higher yields than electron-deficient ones, and a slight decrease of yield was observed when para-substituted aniline was replaced with an ortho-substituted analogue. Finally, pyrrolidinones 4 with various heteroaromatic substituents at nitrogen atom can also be obtained. In conclusion, we offer a straightforward and high-yielding method for the synthesis of previously unknown 2-methylenedihydropyrrolones. [1] A.S. Pankova, P.R. Golubev, I.V. Ananyev, M.A. Kuznetsov, Eur. J. rg. Chem. 2012, 30, [2] P.R. Golubev, A.S. Pankova, M.A. Kuznetsov, Eur. J. rg. Chem. 2014, 17, Authors thank the Russian Scientific Fund for a research grant o

155 P44 THERETICAL IVESTIGATI F PALLADIUM-CATALYZED DIMERIZATI F ALKYES: HYDRPALLADATI VS. CARBPALLADATI PATHWAYS E.G. Gordeev, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry of the Russian Academy of Sciences Catalytic dimerization of terminal alkynes is a waste-free process that allows preparation of enynes within atom-economic transformation. The key question for practical utilization of the dimerization approach is to understand the factors responsible for rendering regioselective transformation and lead in a to a single poduct. The studied catalytic dimerization of terminal alkynes may involve two mechanisms: hydropalladation and carbopalladation, which results in two types of products - head-to-head and head-to-tail dimers. Experimentally it has been found that the presence in the reaction mixture of carboxylate anion direct the reaction to head-to-tail product only [1]. To reveal the mechanistic picture we have carried out the quantum-chemical modeling (B3LYP/6-311G (d) & SDD) of the catalytic dimerization of phenylacetylene including participation of the carboxylate anion. Theoretical calculations have shown that in the absence of carboxylate anion the reaction proceeds as hydropalladation and forms head-to-head product, since potential barrier of the hydropalladation rate-determining step is much smaller than the barrier of the carbopalladation rate-determining step. The predominant formation of head-to-head product was also determined by kinetic factor: the energy of the corresponding transition state was smaller as compared to the transition state of carpbopalladation pathway. When carboxylate anion (acetate ion was used for modeling) was added to the reaction mixture, the H lignad at the metal center was blocked that and only carbopalladation pathway become possible. Indeed, coordination of the carboxylate ion to the palladium atom, leading to the formation of the ion pair, destabilized head-to-head intermediate complex. As a result, the second phenylacetylene molecule was not able to enter into the metal coordination sphere. In the case of head-to-tail intermediate complex such destabilization did not take place. Theoretical study of complete potential energy surface and comparison with experimental data will presented and discussed. References. [1] Zatolochnaya.V., Gordeev E.G., Jahier C., Ananikov V.P., Gevorgyan V., Carboxylate Switch between Hydro- and Carbopalladation Pathways in Regiodivergent Dimerization of Alkynes, Chem. Eur. J., 2014, DI: /chem Acknowledgement. Cooperation with V. Gevorgyan (UIC, Chicago) and his group is greatly acknowledged in this project. The support of the Russian Foundation for Basic Research (RFBR ) is gratefully acknowledged. 155

156 P45 CRSS-METATHESIS F PLYRBREE AD PLY(1- CTEYLEE) AS A EW RUTE T RBREE AD CYCLCTEE MULTIBLCK CPLYMERS M.L. Gringolts, Yu.I. Denisova, G.A. Shandryuk, L.B. Krentsel, A.D. Litmanovich, Ya.V. Kudryavtsev, E.Sh. Finkelshtein A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Russia orbornene (B) and cyclooctene (CE) are well-known objects in ring-opening metathesis polymerization (RMP). Their homopolymers synthesized by RMP are important commercial products [1]. Polynorbornene (PB), which is sold under the trademark orsorex, has various special applications. Poly(1-octenylene) (PCE), known as Vestenamer or polyoctenamer, possesses unusual properties for an elastomer. At the same time, the RMP synthesis of B-CE copolymers is rather difficult because of considerably different polymerization activities of the comonomers. This problem can be solved by catalyst modification [2] or using B with substituents decreasing its activity [3]. We propose a new approach to the synthesis of B-CE multiblock copolymers via interchain cross-metathesis of PB and PCE. That approach enabled us to obtain new copolymers using the 1st generation Grubbs catalyst Cl 2 (PCy 3 ) 2 Ru=CHPh, which is not suitable for copolymerization of B and CE. C E - C E m P C E + [R u = C H P h ] n C H C l 3 a 6 b B - B B -C E C E -C E c B - B P B Cross-metathesis between PB and PCE has been successfully realized. ew B-CE multiblock copolymers were identified and characterized by MR spectroscopy, GPC, and DSC methods. It was found that in the course of the reaction the average lengths of PB and PCE blocks were decreased, as well as the copolymer molecular weight and crystallinity. For copolymer of 1:1 composition, T g, is about -30 o C, which is higher than for PCE (- 80 o C) and lower than for PB (39 o C). The exchange degree (conversion) reached approximately 40-50% in 24 h. Copolymer characteristics can be controlled by varying concentration of the catalyst. The work was supported by RFBR (project ) 1. KJ Ivin, JC Mol (1997) lefin Metathesis and Metathesis Polymerization. Academic Press, London 2. Marc Bornand und Peter Chen Angew. Chem. 2005, 117, C.S. Daeffler and R.H. Grubbs Macromolecules 2013, 46,

157 P46 SELECTIVE C= HYDRGEATI F EES, EALS, AD EATES D.G. Gusev, D. Spasyuk Wilfrid Laurier University, Department of Chemistry, Waterloo, Canada In the past three years, 1-4 we developed catalysts 1-3 for the reduction of esters under hydrogen gas. Complexes 2 and 3 are today s most efficeint catalysts for this process and have recently become commercially available (Aldrich catalogue numbers and ). Here, we disclose the synthetic, structural, and catalytic details of our newest robust, practical, and efficient H 2 hydrogenation catalyst, distinguished by excellent carbonyl selectivity. The air-stable osmium complex from our laboratory, shcl(c)(p-tbu) (4), is today's most successful general catalyst for production of unsaturated alcohols from enals, enones, and alkyl enoates under H 2 at C, while using mol% [s] preferably without solvent. References 1. Goussev, D. G.; Spasyuk, D. PCT Patent Application W 2013/ A1. 2. Spasyuk, D.; Smith, S.; Gusev, D. G. Angew. Chem. Int. Ed. 2013, 52, Spasyuk, D.; Gusev, D. G. rganometallics 2012, 31, Spasyuk, D.; Smith, S.; Gusev, D. G. Angew. Chem. Int. Ed. 2012, 51,

158 P47 VERCMIG SELF-DESTRUCTIVE REACTIVITY I RGALATHAIDE CMPLEXES P.G. Hayes, K.R.D. Johnson, B.L. Kamenz University of Lethbridge, Department of Chemistry, Lethbridge, Canada In an effort to prepare organometallic lanthanide complexes that feature new and unusual properties, we have designed and synthesized several families of pincer ligands comprised of phosphinimine donors attached to rigid aromatic cores. Rare earth complexes of the ligands have been prepared and notably, diverse reaction behavior, such as cyclometalative C H bond activation, dearomatization and functionalization of ligand pyrimidine rings by 1,5-alkyl migration, and ringopening insertion has been observed. otably, the evolution of the design of these pincer ligands has recently yielded a series of thermally stable organolanthanide species that are resistant to cyclometalation. The synthesis, as well as the reaction chemistry of the corresponding organometallic complexes, will be presented.. 158

159 P48 METALLPRPHYRI-ICRPRATED DIPHSPHIE LIGADS FR METAL I-BIDIG G.-A. Yu, K.-M. Wong, J.-S. Huang,. Zhu, C.-M. Che The University of Hong Kong, Department of Chemistry, Hong Kong Diphosphine ligands have been widely used in organometallic chemistry and catalysis. 1 By incorporation of functional units such as metallomacrocycles, the resulting functionalized diphosphines could exhibit unusual properties or binding behavior. In this study, we prepared several examples of ruthenium porphyrin phosphine complexes [Ru II (Por)(dppm) 2 ] (1; Por = TTP, 4-Me-TPP, F 20 -TPP; dppm = bis(diphenylphosphino)methane) by a similar method to that previously reported for their congeners. 2 Reaction of complexes 1 with a number of metal complexes ML n afforded [(L m M)( -dppm)ru II (Por)( -dppm)(ml m )] (2; M = Ag, Au), which have been characterized by spectroscopic methods including 1 H MR, 31 P MR, and UV/Vis spectroscopy, and also by X-ray crystal structure determination. The formation of complexes 2 from complexes 1 demonstrates the role of complexes 1 as a unique type of diphosphine ligands functionalized with metalloporphyrins (which constitute a large family of metal complexes that resemble heme cores in biological systems and exhibit a wide variety of applications 3 ). Studies are underway to explore the properties of this new type of metalloporphyrin-incorporated diphosphine complexes of transition metals. References 1 (a) Genet, J.-P.; Ayad, T.; Ratovelomanana-Vidal, V. Chem. Rev. 2014, 114, (b) Broda, H.; Hinrichsen, S.; Tuczek, F. Coord. Chem. Rev. 2013, 257, 587. (c) Birkholz, M.-.; Freixa, Z.; van Leeuwen, P. W.. M. Chem. Soc. Rev. 2009, 38, (d) Freixa, Z.; van Leeuwen, P. W.. M. Coord. Chem. Rev. 2008, 252, (e) Tuczek, F. Adv. Inorg. Chem. 2004, 56, 27. (f) Bessel, C. A.; Aggarwal, P.; Marschilok, A. C.; Takeuchi, K. J. Chem. Rev. 2001, 101, Ball, R. G.; Domazetis, G.; Dolphin, D.; James, B. R.; Trotter, J. Inorg. Chem. 1981, 20, (a) Handbook of Porphyrin Science, Kadish, K. M.; Smith, K. M.; Guilard, R., Eds.; World Scientific, (b) The Porphyrin Handbook, Kadish, K. M.; Smith, K. M.; Guilard, R., Eds.; Academic Press,

160 P49 SYTHESIS F VEL ACCEPTR MLECULES F M- AD MULTIADDUCT FULLEREE DERIVATIVES FR IMPRVIG PHTVLTAIC PERFRMACE H.B. Liu, C. Liu Institute of Chemistry, Chinese Academy of Sciences,CAS Key Laboratory of rganic Solids, Beijing, P.R. China Fullerene derivatives are extensively used in organic photovoltaics (PVs) because of their high electron affinity and high mobility 1 and remarkable properties on photoinduced electron transfer, in which [6,6]-phenyl C 61 -butyric acid methyl ester (PC 61 BM) is the most widely employed material. 2 We have successfully synthesized and separated a series of tert-butyl 4-C61-benzoate (t-bcb) organofullerenes, including monoadduct, diadduct, and triadduct compounds, and investigated their photophysics, electrochemistry, thermal properties, and high-performance liquid chromatography analysis. 3 The photovoltaic devices were fabricated based on monoadduct, diadduct, and triadduct products, and the devices based on them exhibited power conversion efficiencies of 2.43%, 0.48%, and 1.68%, respectively. Methyl 4-C 61 -benzoate series fullerene materials with low cost and high yield, including monoadduct and bisadduct compounds were also synthesized and the photovoltaic devices based on them showed power conversion efficiency of 3.48% and 0.16% respectively. 4 This was the first time to study the dependent relationship on the device performance and the different isomer numbers. This work supplied new route to design fullerene materials as PCBM s alternative. References 1. Yu, G.; Gao, J.; Hummelen, J. C.; Wudl, F.; Heeger, A. J. Science, 1995, 270, Liu, C.; Xiao, S.; Shu, X.; Li, Y.; Xu, L.; Liu, T.; Yu, Y.; Zhang, L.; Liu, H.; Li, Y. ACS Appl. Mater. Interfaces, 2012, 4(2), Liu, C.; Xu, L.; Chi, D.; Li, Y.; Liu, H.; Wang, J. ACS Applied Materials & Interfaces, 2013, 5, Liu, C.; Li, Y. J.; Chi, D.; Chen, S. H.; Liu, T. F.; Wang, J. Z.; Liu, H. B.; Li, Y. L. Fullerenes, anotubes, and Carbon anostructures, 2014, 22,

161 Intens. [a.u.] Intens. [a.u.] Intens. [a.u.] P50 THE FIRST EXAMPLE F THE SYTHESIS AD STUDY F 2-[(Z)-1- (FERRCEYLMETHXY)PRP-1-EYL]-5-ETHEYLIDEE-4,5- DIHYDR-1,3-THIAZLES BY METHD F MALDI MASS SPECTRMETRY.V. Inozemtseva,.A. Tarasova,.A. edolya, L.V. Klyba, E.R. Sanzheeva, B.A. Trofimov A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk , Russian Federation Earlier unknown 2-[(Z)-1-(ferrocenylmethoxy)prop-1-enyl]-5-ethenylidene-4,4-dimethyl-4,5- dihydro-1,3-thiazole (1), the first representative of ferrocenyl-substituted functionalized 2- thiazolines, was obtained in two preparative steps from (ferrocenylmethoxy)allene, isopropyl isothiocyanate, and propargyl bromide (through synthesis and structural reorganization of conjugated 2-aza-1,3,5-triene 2 under action of t-bua) in 33% yield (not optimized). It was shown that the matrix-assisted laser desorption/ionization (MALDI) mass spectrometry can be appropriate for the study of the low molecular weight thiazoles, in particular, such as compound 1 (with 2,5-dihydroxybenzoic acid as a matrix). In the gas phase under the experiment conditions, the generation of [2M] and [2M H 2 ] ions (M is molecule of thiazole 1) was detected. The analysis of the fragmentation of these ions in field-free region showed that their decay was mainly due to both the degradation of thiazole ring and the formation of the ion [FcCH 2 ] + at m/z x B M m/z M - H 2 x A m/z m/z Mass spectrum MALDI (under the positive mode) of thiazole 1, registered in the mode reflectron. n the inserts: А the МS 2 spectrum of ion at m/z 768, B the МS 2 spectrum of ion at m/z 786. The authors are grateful for the financial support from the Russian Foundation for Basic Research (Grant o a). 161

162 P51 SYTHESIS AD MASS SPECTRA F ELECTR AD CHEMICAL IIZATI F 2-[(Z)-1-METHXYPRP-1-EYL]-5-ETHEYLIDEE- 4,5-DIHYDR-1,3-THIAZLE.V. Inozemtseva, L.V. Klyba, E.R. Sanzheeva,.A. edolya,.a. Tarasova, B.A. Trofimov A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk , Russian Federation The behavior of 2-[(Z)-1-methoxyprop-1-enyl]-5-ethenylidene-4,5-dihydro-1,3-thiazoles 1 4, synthesized for the first time from methoxyallene, isothiocyanates, and propargyl bromide, 1 under electron ionization (EI, 70 ev) and positive ion chemical ionization (PICI, methane) has been studied. Principal fragmentation routes of the 4,5-dihydro-1,3-thiazoles 1 4 after EI include a thiazole ring cleavage (pathway 1) and the loss of alkyl substituent, mainly at position 4 (pathway 2). For PICI of the compounds 1 4 are typical processes of protonation and electrophilic addition followed by the loss of the 2-methoxybut-2-enenitrile molecule. The authors are grateful for the financial support from the Russian Foundation for Basic Research (Grant o a). 1. edolya,. A.; Tarasova,. A.; Albanov, A. I.; Trofimov, B. A. Tetrahedron Lett. 2014, 55,

163 P52 FLURESCECE PHTSESITIVE MATERIALS FR IFRMATI PTICAL RECRDIG V.F. Traven, I.V. Ivanov, S.M. Dolotov, D.A. Cheptsov D. Mendeleev University of Chemical Technology of Russia In the modern world, computer and information technology continue to develop with increasing speed, that increases the requirement for higher performance systems that are capable of preservation, reproduction and processing of information at very high speeds. An actively developing area, allowing to obtain a carrier with high density recorded information is to manufacture fluorescent multilayer disks (FMD). Use of the information recording FM-discs is based on photochemical conversion of compounds that change their fluorescent properties, whether it is shift of the maximum fluorescence, appearance of fluorescence or its attenuation. [1] R 1 R 3 R 2 h CCl 4 R 1 R 3 R 2 +H + C H 3 C H 3 C H 3 C H 3 C H 3 H 3 C + C H 3 H + C H 3 H Previously, we have studied new reaction photodehydrogenation 3-pyrazolinylcoumarines and found it be accompanied by increased acidity [2]. In this report, we consider an application of this reaction for opening of the lactone form of rhodamine dye. These two reactions are accompanied by the formation of the fluorophore with a high fluorescence quantum yield and high light resistance. As we have found both these reactions undergo easily both in organic solvents and in polymer matrixes. For example, the irradiation of the polymethylmethacrylate film which contain dissolved pyrazoline, hexachloroethane and lactone of Rhodamine B by light in a wavelength range of nm leads to the appearance coloration of the film with irradiated areas exhibits fluorescent properties. We have used these results for optical data recording with fluorescent readout. [3] 1). C. M. Rudzinski, D.G. ocera, In ptical Sensors and Switches; K.S. Schaze, Ed.; Marcel Dekker: ew York, USA, 2001 (Chap. 1). 2). I.V. Ivanov, S.M. Dolotov,.I. Kobeleva, T.M. Valova, V. A. Barachevskii, V.F. Traven, Izv.RA, Ser.khim. 2012, ). V. F. Traven, S. M. Dolotov, I. V. Ivanov, V. A. Barachevsky,. I. Kobeleva, T. M. Valova, I. V. Platonova, A.. Ait, Patent application no of March 17, 2011; 163

164 P53 RIG PEIG F DR-ACCEPTR CYCLPRPAES WITH AZIDE I STRAIGHTFRWARD ACCESS T AZA-HETERCYCLES K.L. Ivanov, E.V. Villemson, E.M. Budynina,.A. Ivanova, I.V. Trushkov Moscow State University, Department of Chemistry, Moscow, Russia ucleophilic ring opening of donor-acceptor (DA) cyclopropanes is an efficient approach to various polyfunctional structures, including natural products and medicines. 1-4 Currently, a wide range of nucleophiles was introduced into reactions with DA cyclopropanes; however, a number of nucleophilic reagents still remains unexplored. In this research, we have found optimal conditions for DA cyclopropanes 1 ring opening with azide ion leading to the formation of -azidocarbonyl compounds 2. Moreover, we developed one-pot process consisting of ring opening/krapcho dealkoxycarbonylation which allowed us to achieve a simple approach to the GABA precursors 3. The concurrent presence of azide function, activated methine or methylene group, EDG and EWG substituents in compounds 2 and 3 makes them convenient building blocks for the streamlined synthesis of wide range five- and six-membered -heterocyclic frameworks which are ubiquitous structural units of numerous natural and synthetic bioactive molecules. We designed approaches to pyrrolidones, pyrroles, piperideines, triazolopyridines, tetrazolopyridines, etc. based on simple synthetic sequences including Staudinger/aza-Wittig cascade or [3+2] cycloaddition as key steps. These strategies were successfully used in formal syntheses of nicotine and atorvastatin. 1. Reissig H.-U., Zimmer R., Chem. Rev. 2003, 103, Carson C.A., Kerr M.A., Chem. Soc. Rev. 2009, 38, Cavitt M.A., Phun L.H., France S., Chem. Soc. Rev. 2014, 43, Schneider T.F., Kaschel J., Werz D.B., Angew. Chem. Int. Ed. 2014, 53,

165 P54 ATURAL GAS HYDRATE FRMATI I THE PRESECE F SURFACTATS I.K. Ivanova 1, M.E. Semenov 2, I.I. Rozhin Ammosov orth-eastern Federal University 2 - Institute of il and Gas Problems, Siberian Branch, Russian Academy of Sciences The aim of the work is determination of the temperature and pressure of formation and decomposition (melting) of the natural gas hydrate synthesized from natural gas of the Sredneviluy gas and condensate field (GCF) and distilled water also in the systems based on it: in the presence of sulfonic of 0,1% by weight, as well as with artificial nucleating agent (sand) by differential scanning calorimetry. Fig. 1 Calculated equilibrium conditions of the gas hydrate formation for natural gas of the Sredneviluy GCF and methane The experimental data (Fig. 1) are identical to those calculated by the method of E. Dendy Sloan for the used natural gas hydrate equilibrium conditions. It should be noted that against the background stands out experimental points obtained by the decomposition of natural gas hydrate, which was synthesized from a 0,1% solution of sulfonic. Comparing the equilibrium conditions of the individual components of natural gas, it is found that this point corresponds to the equilibrium conditions of the methane hydrate. It is known that natural gas hydrates are a mixture of hydrates of different gases with complex structure. This study suggests the possibility of separation of this mixture on the hydrates of individual gases. Furthermore, it was found that the use of surfactants leads to an increased conversion of water into the gas hydrate (> 70%), compared with 2,3% of the gas hydrate formation in distilled water. 165

166 P55 CTRL F THE REACTI SELECTIVITY I Pd AD i- CATALYZED HYDRPHSPHRYLATI F ALKYES J.V. Ivanova 1, L.L. Khemchyan 1, S.S. Zalesskiy 1, V.P. Ananikov 1, I.P. Beletskaya 2, Z.A. Starikova Zelinsky Institute of rganic Chemistry RAS, Moscow, Russia 2 - Lomonosov Moscow State University, Chemistry Department, Moscow, Russia 3 - esmeyanov Institute of rganoelement Compounds RAS, Moscow, Russia owadays, transition-metal-mediated carbon-heteroatom (C-E: E=S, Se, Si, P, Te, ) bond construction has drawn great attention due to well-recognized advantages: high selectivity, quantitative yields and mild reaction conditions. [1],[2],[3] The study of metal-catalyzed phosphorus-carbon (P-C) bond formation has led to significant progress in organic synthesis and established numerous synthetic procedures for the synthesis of new valuable compounds. [1] We developed two switchable synthetic protocols allowing us to obtain the products of choice via subtle change in the catalytic system (Scheme 1). The palladium-based catalyst demonstrated high sensitivity to the number and position of substituent in the aromatic rings of the phosphine ligand. Application of two different phosphines selectively directed the catalytic reaction either to linear or branched product formation. [4] The i(acac) 2 /DIBAL-H precatalyst was the first example of nickel-based system which allowed to synthesize vinylphosphonates, bisphosphonates or alkyltetraphosphonates without any ligands or solvents. [5],[6] Slight variations of i precatalyst loading routed the selectivity of the hydrophosphorylation reaction. Mechanistic study with ESI-MS and MR methods revealed the key nickel intermediates involved into the catalytic cycle. [6] Scheme 1 [1] V.P. Ananikov, M. Tanaka (Eds.), Hydrofunctionalization, Springer, 2013, Heidelberg. ISB ; DI: / [2] I.P. Beletskaya, V.P. Ananikov, Chem. Rev., 2011, 111, [3] F. Alonso, I.P. Beletskaya, M. Yus, Chem. Rev., 2004, 104, [4] V.P. Ananikov, J.V. Ivanova, L.L. Khemchyan, I.P. Beletskaya, Eur. J. rg. Chem., 2012, [5] Yu.V. Ivanova, L.L. Khemchyan, S.S. Zalesskii, V.P. Ananikov, I.P. Beletskaya Rus. J. rg. Chem., 2013, 49, [6] L.L. Khemchyan, J.V. Ivanova, S.S. Zalesskiy, V.P. Ananikov, I.P. Beletskaya, Z.A. Starikova, Adv. Synth. Catal., 2014, 356,

167 P56 Cu-CATALYZED AERBIC XIDATIVE TRASFRMATI F KETE-DERIVED -TSYL HYDRAZES: A EW ETRY IT ALKYES X.-W. Li, W.-Q. Wu, H.-F. Jiang South China University of Technology, School of Chemistry and Chemical Engineering, Guangzhou, P. R. China Alkyne moiety is a fundamental structural element and functional group occurring in various bioactive molecules, functional materials and natural products. 1 Sonogashira reaction and electrophilic alkynylation 2 are the most widely used methods for the construction of alkynes, still, some formidable challenges remained to be resolved. 3 n the other hand, the field of alkyne retrohydration, that is, deprotonation of ketone derivatives for the alkynes synthesis, however, is still in its infancy. 4 In our continuing efforts toward the development of green chemistry on selective oxidation of unsaturated hydrocarbons, 5 we have developed an efficient copper-catalyzed aerobic dehydrogenation of ketone-derived -tosyl hydrazones which were carbene precursors, to the corresponding alkynes. Further cross-couplings of -tosyl hydrazones with halides or terminal alkynes were also performed, delivering to functionalized alkynes or asymmertric diynes. A mechanism involved aerobic oxidation of Cu-carbene intermediate was proposed for this C-C triple bond formation. Reference: 1. Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH, Weinheim, Germany, Dudnik, A. S.; Gevorgyan, V. Angew. Chem. Int. Ed. 2010, 49, egishi, E.; Anastasia, L. Chem. Rev. 2003, 103, egishi, E.; King, A..; Klima, W. L.; Patterson, W.; Silveira, A. J. rg. Chem. 1980, 45, Wu, W.; Jiang, H. Acc. Chem. Res. 2012, 45,

168 P57 [Co]-СATALYZED [6+2]-CYCLADDITI F 1,2-DIEES T 1,3,5,7- CYCLCTATETRAEE V.A. Dyakonov 1, G.. Kadikova 1, G.F. Gazizullina 2, U.M. Dzhemilev Federal State Institution of Science Institute of Petrochemistry and Catalysis, Russian Academy of Sciences; Laboratory catalytic Synthesys; Ufa; Russia 2 - Ufa State University of Economics and Service; Ufa; Russia Eight-membered carbocycles are found in many natural compounds exhibiting high biological activity [1]. The catalytic cycloaddition based on 1,3,5,7-cyclooctatetraene (CT) are an effective method for the synthesis of such carbocycles [2]. [Co]-Catalyzed cyclodimerization of CT with alkynes leading to the formation of bicyclo[4.2.2]deca-2,4,7,9-tetraenes 1 [3]. R C o I 2 /d p p e/z n/z ni 2, 40 o C, C 2 H 4 Cl 2 1 It should be noted that in literature have no examples of catalytic codimerization of 1,3,5,7- cyclooctatetraene with 1,2-dienes. In the development of this work and our ongoing research [4a,b] we carried out [6π+2π]-cycloaddition of CT with 1,2-dienes in the presence of 10 mol% CoI 2 /dppe/zn/zni 2 (C 2 H 4 Cl 2, 40 C, 20 h). The corresponding bicyclo[4.2.2]deca-2,4,7-trienes 2 were obtained in high yields. R R C o I 2 /d p p e/z n/z ni 2, 40 o C, C 2 H 4 Cl 2 2 R = P h, A lk This work was performed under financial support from the Russian Foundation for Basic Research (Grant and Grant of RF President (Sci. Sh )). 1. Plemenkov V.V. Introduction to the chemistry of natural compounds. Kazan, 2001, 376 p. 2. Yu Z.X, Wang Y., Wang Y. Transition-metal-catalyzed cycloadditions for the synthesis of eightmembered carbocycles, Chem. Asian J., 2010, Achard M., Mosrin M., Tenaglia A., Buono G. Cobalt (ΙΙ)-Catalyzed [6+2] Cycloadditions of Cyclooctatetra(tri)ene with Alkynes, J.rg.Chem, 2006, 71, a) Dyakonov V.A., Kadikova G.., Dzhemilev U.M. Ti-catalyzed [6π +2 π]-cycloadditions of allenes with 1,3,5-cycloheptatriene, Tetrahedron Lett., 2011, 52, ; b) Dzhemilev U.M., Kadikova G.., Kolokoltsev D.I., Dyakonov V.A. Catalytic [6π+2π]-cycloaddition of alkynes, 1,2- and 1,3-dienes to 1,3,5-cycloheptatrienes involving Ti complexes, Tetrahedron, 2013, 69, R 168

169 P58 MBILE ADEFECTS AS CMPLEXIG AGETS I SLID PHASE CHEMISTRY A.M. Kaplan,.I. Chekunaev..Semenov Institute of Chemical Physics, Russian Academy of Sciences Put forward by one of the authors, the idea about the possible role of mobile nanodefects as complexing agents, allowed to explain for the first time a number of non-trivial effects of solidphase chemistry. These are: 1. the effect of greatly acceleration of catalytic processes induced by high energy impacts on heterogeneous catalysts [1]; 2. the phenomena of "freezing" of polymer chains at constant temperatures and "reanimation" of such chains at temperatures increasing of investigated samples in solids [2]; 3. the effect of exceeding by several orders of the rate of affiliation of monomer molecules to the active centers in glass monomers samples compared to crystalline samples of the monomer [3]; 4. the phenomenon of the abnormal logarithmic time dependence of the polymer yield for unterminated solid-state polymerization at low conversions [4]. In contrast to gas and liquid phases, very low orientation mobility of microparticles in solid phase frequently does not allow to perform chemical interaction even particles of reagents which are in contact with each other for prolonged time. This effect is a consequence of unacceptable for chemical interaction starting mutual orientation of the particles and impossibility to improve the situation at insufficient space close to them. Furthermore, structural nanodefects (mobile vacancies, polyvacancies, dislocations, nanoincontinuity, etc) present in the real solid bodies may, in case of their sufficient mobility, lead to pair of potentially chemically capable, but unreacting due to orientational immobility of adjacent reagents particles, in quite dense areas of solid bodies sufficient free space. Remobing by this the steric barrier for the interactions of such particles. Consequently, as it was for the first time mention by the presenter, real ( living ) active center (A*) of solid phase reactions should be considered not the experimentally detectable traditional active centers (A) (radical and ions), but a peculiar complex of such centers with the carrier of excess of volume with mobile nanodefects. The concentration of [A*]<<[A]. It should be pointed out the special role of mobility of nanodefects in formation of real cative centers A*. In case of presence of in the system of only motionless nanodefects, chemical diffusion leads in time to the removal of reacting particles from such defects, turming these particles to inactive state. In heterogenous catalysis this effect is similar to the effect of catalyst poisoning. Movable nanodefects which activated during some time a group of reagent particles, move to another such group, and also activate it. This process of activation of chemical process takes places until meeting of moving nanodefects, leading to sticking of defects and decrease of their concentration. Based on concept of moving nanodefects with excessive free volume as complexing agents, authors using computer calculations in papers [1-4] explained the effects previously considered anomalous mentioned above. 1. A.M.Kaplan, V.V.Lunin,.I.Chekunaev. Book of abstracts of VII Voevodsky conference «Physics and Chemistry of elementary chemical processes». P Chernogolovka A.M. Kaplan,.I. Chekunaev. Doklady Physical Chemistry, Vol. 425, Part 1, pp , A.M. Kaplan,.I. Chekunaev. Russian Chemical Bulletin. o. 8, pp A.M. Kaplan,.I. Chekunaev. Polymer Science. Series B, Vol. 52, o. 1-2, pp ,

170 P59 SYTHESIS F LIGSACCHARIDE FRAGMETS F CADIDA ALBICAS MAA CRRESPDIG T ATIGEIC FACTR 6 A.A. Karelin, Y.E. Tsvetkov,.E. ifantiev. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Laboratory of Glycoconjugate Chemistry, Moscow, Russia The yeast-like fungi of the genus Candida are opportunistic pathogenic microorganisms capable of causing severe infections in immunocompromised patients. The main surface antigen of Candida responsible for its antigenic specificity is mannan, which represents the carbohydrate part of the cell wall mannoprotein. The determinants of antigenic factor 6 are represented by several β-d-man- (1 2)-residues attached to short α-(1 2)-linked chains. Here we report synthesis of oligosaccharides 1 and 2 containing two and three β-linked residues. The presence of the amino group in the aglycones of the synthetic oligosaccharides allows their subsequent covalent binding to high-molecular carriers and labels of various types We utilized a convergent approach based on glycosylation of known α-(1 2)-linked mannosyl acceptor with β-(1 2)-linked donors. The preparation of required donors was started from compound 3. The thiomannoside was transformed into sulfoxide 4. Then these monosaccharides were coupled to give required disaccharide donor. Here we used the fact that conditions of sulfoxide activation don t affect thioglycosides. xidation of dimanosyl donor 5 followed by glycosylation of 3 allowed obtaining trisaccharide donor 7. Glycosylation of α-(1 2)-linked mannosyl acceptor with donors 5 and 7 and subsequent removal of protecting groups gave target olygomannosides 1 and 2. Acknowledgments This work was supported by the Russian Foundation for Basic Research under grant

171 P60 ASTRUCTURED ICKEL RGASULFIDES: SYTHESIS, CHARACTERIZATI AD APPLICATI I THE CATALYTIC CARB-SULFUR BD FRMATI REACTI A.S. Kashin, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry RAS, Moscow, Russia ver the last decades nanostructured metal chalcogenides have made an outstanding contribution to the nanotechnology, microelectronics, optics and material science. However their application in organic synthesis and catalysis remains largely unexplored [1]. In our work we focused on the nickel organosulfides [i(sar) 2 ] n. These nanostructured nickel complex salts can be easily prepared by the reaction between nickel acetylacetonate and aryl thiols. Rapid ligand substitution accompanied with the self-organization in solution leads to formation of polymeric structures, where nickel atoms are linked by μ 2 -SAr groups. Tuning of the reaction conditions or changing of the substituent in the aromatic ring of thiol allows to generate [i(sar) 2 ] n particles of various shapes and sizes (Figure 1). Figure 1. FE-SEM images of [i(sar) 2 ] n particles, Ar = Ph (A), p-brph (B). We have demonstrated that synthesized nickel aryl sulfides can be utilized as a source of SAr groups for the carbon-sulfur bond formation in the cross-coupling reaction with aryl halides [2]. Reaction in the presence of palladium- or copper-based catalytic system results in the diaryl sulfides formation with the yield up to 95% (Scheme 1). Scheme 1. Catalytic C-S bond formation reaction between nickel organosulfides and aryl halides. A unique effect of morphology control of the SAr group donor reactivity in cross-coupling reaction was found. Mechanistic studies have shown that cross-coupling reaction with Cu catalyst proceeds in the liquid phase and involves leaching, whereas the same reaction with Pd catalyst is more complex and may involve both homogeneous and heterogeneous pathways. [1] V.P. Ananikov, I.P. Beletskaya, Dalton Trans. 2011, 40, [2] A.S. Kashin, V.P. Ananikov, Top. Catal. 2013, 56,

172 P61 SYTHESIS F DERIVATIVES F 6-ACETYL-2-CYCLHEXEE AD THEIR BR CHELATE CMPLEXES D.S. Khachatryan 1, I.I. Boyko 2, A.A. Vardapetyan 1, A.L. Razinov 1, K.R. Matevosyan FGU "IREA", Moscow, Russia 2 - ООО "TEHLG", Pereslavl-Zalessky, Russia 3 DI Mendeleev RHTU, Moscow, Russia In some cases, reactions of enolates obtained using conventional basic reagents (alcoholates, amides, metal hydrides) afford products in very low yields 1,2. In the late 70's we first succesfully used patassium carbonate in Michael reaction for the synthesis in preparative quantities of derivatives of 2-cyclohexenone 2-4 synthons for construction of physisologically active molecules, including steroids 1. The present work follows the studies in the field of synthesis of new derivatives of 2-cyclohexenone by Michael reaction in the presence of patassium carbonate. f special interest are derivatives of 2- cyclohexenone containing acetyl substituent in position 6 analogues of 1,3-diketones which can complex transition and rear yearth metals 5-7. We studied prepartion of 3,5-disubstituted 6-acetyl-2-cyclohexenones, based on cyclocondensation reaction of acetylacetone (1) with α,β-unsaturated ketones 2а-h in the presence of catalytic amount of patassium carbonate at reflux in different solvents. M e M e + R 1 R 1 2 a -h 3 a -h 4 a -h а R=MeC 6 H 4 CH=CH; R 1 =MeC 6 H 4 ; b R=R 1 =Ph; c R=2-тиенил, R 1 =Ph; d R=2,4-Cl 2 C 6 H 3 CH=CH, R 1 =BuC 6 H 4 ; e R=4-BuC 6 H 4 CH=CH; R 1 =4-BuC 6 H 4 ; f R=4-AmC 6 H 4 CH=CH; R 1 =4-AmC 6 H 4 ; g R=4-lC 6 H 4 CH=CH; R 1 =4-ClC 6 H 4 ; h R=4-MeC 6 H 4 CH=CH;R 1 =4-MeC 6 H 4 In 1 Н MR spectra of all diketones 4a-h, the doubling of all expected signals is observed that, as known 7, is due to keto-enol tautomerism, i.e. 6-acetyl-2-cyclohexenones behave in solution as classic 1,3-diketones. Based on these data, the chelating ability of compounds 4a-h was evaluated. It was shown that they can form chelate complexes with boron 1,3-dioxaborines, which possess photosensibilizing properties 5, as well as (with compound 4b as an example) complexes with metals (Сu 2 +, i 2+, Со 2+, Еu 3+ ) 4,6. 1 E.D. Bergmann, D.Ginsburg, R.Pappo, in rganic Reactions, v.10, Wiley, ew York, M.Morlyan, D.S. Khachatryan, Sh.. Badanyan, Arm. Chem. J. 1978, 31 (2) D.S. Khachatryan, A.A. Vardapetyan, G.A. Panossian, R.G. Mirzoyan,.M. Morlyan, ZhrH. 1990, 26 (10), D.S. Khachatryan, A.A. Vardapetyan, V.. Tkachenko,.M. Morlyan, Proc. Conf., «III All-Union Conference on Chemical reagents", Ashgabat, 1989, p I.I. Boyko, T.I. Boyko, A.A. Vardapetyan, G.V. owicka, D.S. Khachatryan,.M. Morlyan and K.K. Koshelev. A.s USSR; Bull. Izobr., 2000, V.I.Zelenov, Russian J.Gen.Chem (1), J.K.F.Geirsson, A.D.Gudmundsdottir, Synthesis, 1990, 11, 993. R 1 M e M e R R 1 R M e 172

173 P62 TRITERPEID SAPIS FRM THE RTS F ACATHPHYLLUM GYPSPHILIDES REGEL AS PTETIAL IMMUE-MDULATIG TLS FR DEDRITIC VACCIE DESIG E.A. Khatuntseva 1, V.M. Men shov 1, A.S. Shashkov 1, Y.E. Tsvetkov 1, R.. Stepanenko 2, R. Ya. Vlasenko 2, E.E. Shults 3, G.A. Tolstikov 3, T.G. Tolstikova 3, D.S. Baev 3, V.A. Kaledin 4,.A. Popova 4, V.P. ikolin 4, P.P. Laktionov 5, A.V. Cherepanova 5, T.V. Kulakovskaya 6, E.V. Kulakovskaya 6,.E. ifantiev D. Zelinsky Institute of rganic Chemistry, RAS, Leninsky pr. 47, Moscow, RF 2 - Institute of Immunology, Ministry of Health and Social Development of RF, Kashirskoe Ch., 24/2, Moscow, RF Vorozhtsov ovosibirsk Institute of rganic Chemistry, Siberian Branch of RAS, pr. Acad. Lavrent eva, 9, ovosibirsk, RF 4 - Institute of Cytology and Genetics Siberian Branch of the RAS, 10 pr. Acad. Lavrent eva, ovosibirsk, RF 5 - Institute of Chemical Biology and Fundamental Medicine, Siberian Branch of the RAS, 8 pr. Acad. Lavrent eva, ovosibirsk, RF 6 - G. K. Skryabin Institute of Biochemistry and Physiology of Microorganisms, RAS, Pushchino Despite significant effort, the development of effective vaccines inducing strong and durable T-cell responses against cancer cells has remained a challenge. It is anticipated that the main target of vaccination are dendritic cells, the principal antigen presenting cells, whose main function is to identify exogenous structures and present them to naïve CD4+ and CD8+ T cells in lymph nodes. A current strategy to enhance the effectiveness of vaccination is to deliver antigens directly to dendritic cells, which are readily accessible within the well-established in vitro procedure. Anticancer dendritic vaccines are intended to activate cytotoxic antigen-specific CD8 + T cells, which are activated via complexes with MHC class I molecules of DCs, with the only possibility of exogenous antigen presentation on those to be done by cross-presentation. This process includes translocation of the antigen from the endosome to the cytosol and is known to be efficiently promoted by saponins, which are part of saponin-based adjuvants QS21 and ISCMATRIX. Amphiphilic nature of most saponins enables the formation of nano-sized micelles, and among them immune-stimulating complexes (ISCM), which are currently used as adjuvant systems. These particles are known to be readily engulfed by DCs and the optimal uptake of this type of vesicles by DCs was reported to be achieved when particle size is μm, which corresponds to conventional size of saponin-based micelles in water solutions. The objective of the present work was to isolate new individual saponins from readily available routs of Acanthophyllum gypsophiloides with the view to further investigation of their vesicle formation potential and in vitro effect of saponin-containing ISCM s on dendritic cells. Two new triterpenoid saponins 1 and 2 were isolated from the methanol extract of the roots of Acanthophyllum gypsophiloides Regel. These saponins have quillaic acid or gypsogenin moieties as aglycon and both bear similar sets of two oligosaccharide chains, which are trisaccharide -L- Ara-(1 3)-[ -D-Gal-(1 2)]- -D-GlcA and pentasaccharide -D-Xyl- (1 3)- -D-Xyl-(1 3)- -L-Rha-(1 2)-[ -D-Qui-(1 4)]- -D-Fuc connected to C-28. The structures were elucidated by the combination of 1 R = H; 2 R = H mass spectrometry and 2D MR spectroscopy methods. Reference: E.A. Khatuntseva et al., Beilstein J rg Chem. 2012,8:

174 P63 MR SPECTRSCPY AD ESI-MS AS EFFECTIVE RAPID METHDS FR MITRIG BIMASS CVERSI IT 5-HMF I IIC LIQUIDS E.A. Khokhlova, V.V. Kachala, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia Unprecedented selectivity for biomass and cellulose conversion to 5-HMF has opened outstanding opportunities for sustainable chemical industry. 5-HMF was identified as a "platform chemical" for production of biofuels, solvents, resins, liquid alkanes (C 7 - C 15 ), and monomers for plastics. However, in spite of complete conversion, more detailed studies have shown moderate product yields (40-60%), and later, formation of by-products (humins) has been identified. The main stumbling block to studying cellulose processing in ionic liquids is the absence of an analytic tool for monitoring reaction yields in ionic liquids.[1] ur research has been focused on real-time carbohydrate conversion monitoring using a new MR based approach for quantitative measurements. A practical application of the developed approach was demonstrated directly in the MR tube. ur latest study revealed the ways to characterize molecular transformations in IL systems and to detect reaction intermediates using a special reactor that eliminates microheterogeneity.[2] Transformation of carbohydrates to 5-HMF with various promoters was investigated and discrepancy between conversions and yields was observed. Highquality MR spectra suitable for integration of individual signals were measured after removing the intrinsic heterogeneity of ionic liquid samples below the spectroscopic detection level. Moreover, we have disclosed a new opportunity of using the MS2 mode in reaction monitoring frameworks that make it possible to obtain both qualitative and quantitative information. A combined use of the developed MR and mass spectrometry approaches for analyzing components of IL solutions will expand the frames of promising chemistry in ILs. [1] V.P.Ananikov, Chem. Rev. 2011, 111, 418. [2] E.A.Khokhlova, V.V.Kachala, V.P.Ananikov. ChemSusChem, 2012, 5,

175 P64 Rh(III) CATALYZED SYTHESIS F ISQUILIE DERIVATIVES BY AULATI F BEZYLAMIES WITH ALKYES D.-S. Kim, C.-H. Jun Yonsei University, Department of Chemistry, Seoul, Korea Rh(III)-catalyzed C-H bond cleavage is one of efficient ways to make -heterocyclic compounds. 1 In particular, ortho-alkyl- or alkenylation provides an efficient synthetic method for preparing ortho-substituted aromatic ketones. 2 During the course of our studies on the Rh(III)-catalyzed - annulation reaction, we found synthetic method of pyridine derivatives from primary allylamines with alkynes. 3 In this poster, we report a new protocol for the preparation of isoquinoline from benzylamine and internal alkyne using Rh(III)-catalyst with Cu(II) as an oxidizing agent. For example, the -heterocyclic annulation reaction of 2-methoxybenzylamine with 4-octyne was carried out at 100 o C for 4 hours in the presence of [Cp * RhCl 2 ] 2 (2.5 mol% [Rh]) and Cu(Ac) 2. H 2 to produce corresponding pyridine in 92% yield. The proposed mechanism of this annulation reaction is also discussed Song, G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, Murai, S.; Kakiuchi, F; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M. Chatani,. ature, 1993, 366, Kim, D.-S.; Park, J.-W.; Jun, C.-H. Chem. Commun. 2012, 48, Kim, D.-S.; Park, J.-W.; Jun, C.-H. Adv. Synth. Catal. 2013, 355,

176 P65 A VEL BRACHED MSACCHARIDE, 3,6-DIDEXY-4-C-[(S)-1,2- DIHYDRXYETHYL]-D-XYL-HEXSE, FRM A PLYSACCHARIDE F A BACTERIUM F THE GEUS PHTRHABDUS.P. Arbatsky 1, A.S. Shashkov 1,.A. Kirsheva 2, A.. Kondakova 1, R.Z. Shaikhutdinova 2, S.A. Ivanov 2, A.P. Anisimov 2, Y.A. Knirel D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - State Research Center for Applied Microbiology and Biotechnology, bolensk, Moscow Region, Russia The genus Photorhabdus from the family Enterobacteriaceae includes three species of entomopathogenic bioluminescent bacteria Photorhabdus temperata, Photorhabdus luminescens, and Photorhabdus asymbiotica. They all have a mutualistic relationship with entomophagous nematodes from the family Heterorhabditis. These bacteria synthesize an S-form lipopolysaccharide, which consists of lipid A, core oligosaccharide, and -specific polysaccharide (-antigen) and is important for both pathogenicity and symbiosis. Recently, aiming at creation of the chemical basis for classification of Photorhabdus species, structures of the -polysaccharides of representatives of P. asymbiotica subsp. asymbiotica and subsp. australis 1 and P. luminescens subsp. laumondii 2 have been elucidated. In this work, we established the -polysaccharide structure of P. temperata subsp. temperata Xlach T and identified a novel branched monosaccharide as its component. The -polysaccharide was obtained by mild acid hydrolysis of the lipopolysaccharide isolated from bacterial cells by phenol-water extraction. In addition to monosaccharides that are rather common in nature (glucose, mannose, galactose, and -acetylgalactosamine), sugar analysis of the -polysaccharide revealed a branched octose called photorhabdose. The new sugar was isolated as a 1,2 -anhydro furanose derivative by reversed-phase HPLC after full acid hydrolysis of the -polysaccharide (Scheme), and its structure as 3,6-dideoxy-4-C-[(S)-1,2 -dihydroxyethyl]-d-xylohexose was determined by one- and two-dimensional 1 H and 13 C MR spectroscopy. Photorhabdose has not been hitherto found in nature and differs from the known branched octoses, 3,6-dideoxy-4-C-[(S)- and (R)-1-hydroxyethyl]-D-xylo-hexoses (yersinioses A and B, respectively), in deoxygenatation of the terminal carbon (C-2 ) of the side chain. Scheme. Isolation of photorhabdose (Sug) by full acid hydrolysis of the -polysaccharide. Arrows indicate H,H correlations observed in the ESY spectrum. 1. Kondakova, A..; Kirsheva,. A.; Shashkov, A. S.; Shaikhutdinova, R. Z.; Arbatsky,. P.; Ivanov, S. A.; Anisimov, A. P.; Knirel, Y. A. Carbohydr. Res. 2011, 346, Kondakova, A..; Kirsheva,. A.; Shashkov, A. S.; Shaikhutdinova, R. Z.; Ivanov, S. A.; Anisimov, A. P.; Knirel, Y. A. Carbohydr. Res. 2012, 351,

177 P66 EVLUTI AD ITERLAYER DYAMICS F ACTIVE SITES F PRMTED TRASITI METAL SULFIDE CATALYSTS UDER HYDRDESULFURIZATI CDITIS V.M. Kogan 1, P.A. ikulshin 2,.. Rozhdestvenskaya D. Zelinsky Institute of rganic Chemistry, RAS, Laboratory of catalysis by trasition metals and their compounds, Moscow, Russia 2 - Samara State Technical University, Samara, Russia According to the suggested dynamic model [1], neighboring layers of the multilayered MoS 2 crystallite exchange sulfur between Mo- and S-edges placed one under another in the course of permanent reduction sulfidation processes under hydrogen atmosphere. When the sulfur atoms bonded to Co atoms leave the reduced edge of the layer, the atoms of the promoter also move along the sulfur atoms from one layer to an adjacent layer of higher sulfidation state. Then the process reverses. Such oscillations occur until the sulfur organic compound adsorbs on the vacancy on the reduced edge. The frequency of the oscillations determines catalytic activity of the CoMoS slab. Thiophene adsorption makes transfer of a promoter to the neighboring slab improbable because the electron density of thiophene sulfur compensates the extra positive charge on the Mo atom appeared after H 2 S removal. When thiophene adsorbs on the vacancy of the CoMoS site the proton linked to Co moves to the SH group of the neighboring layer forming the H 2 S which desorbs from this layer and new vacancy is formed. This model explains the reasons of the electron transfer from atom of promoter to Mo and different locations of the active sites responsible for hydrogenation and desulfurization on a promoted Mo-sulfide slab. A method to evaluate the efficiency of CoMoS catalysts for HDS of various types of crudes has been developed. ow these findings obtain their explanations within the developed dynamic model (Fig. 1). Fig. 1. Dynamic model of transformations of the active sites of promoted TMS catalysts in the course of thiophene HDS. The suggested model gives a basis to develop criteria to evaluate the efficiency of the catalyst activity in hydrotreating of various types of crude oil. 1. V.M. Kogan, P.A. ikulshin,.. Rozhdestvenskaya, Fuel 100 (2012)

178 P67 THE CCEPT F ITERLAYER DYAMICS AD THE MECHAISMS F HDS AD ALCHL SYTHESIS THE ACTIVE SITES F PRMTED TMS CATALYSTS V.M. Kogan 1, P.A. ikulshin 2, V.S. Dorokhov D. Zelinsky Institute of rganic Chemistry, RAS, Laboratory of catalysis by trasition metals and their compounds, Moscow, Russia 2 - Samara State Technical University, Samara, Russia A new mechanistic model for molybdenum sulfide catalysts with cobalt and nickel promoters under hydrodesulfurization (HDS) reaction conditions is proposed that includes dynamic migration of sulfur and promoter atoms between adjacent sulfide layers [1,2]. These migrations are caused by heterolytic dissociation of gas-phase hydrogen and formation of hydride hydrogen on a promoter atom. Hydride hydrogen adsorbed on a promoter induces electron density transfer from the bonding promoter to Mo, changing its catalytic activity. Adsorbed hydrogen induces migration of sulfur and promoter atoms between adjacent clusters. This dynamic migration causes transformation of rapid into slow sites and vice versa and, therefore, influences catalytic activity. Migration of Co or i promoter atoms to Mo sites on the rim is more likely than to Mo sites on the edge of Co(i)MoS layers because the former can accept promoter atoms from both upper and lower layers. A method to evaluate the efficiency of CoMoS catalysts for HDS of various types of crudes has been developed. The proposed model provides crutial information for rational design of improved hydrotreating catalysts and selection of preferred catalytic reaction conditions for various types of hydrocarbon feedstock via optimization of the density and ratio of rapid and slow catalyst active sites. Application of the dynamic model to the investigation of the mechanism of the mixed alcohol synthesis (MAS) over TMS catalysts modified by potassium gives us ground to assume that the reaction of alcohol formation from synthesis gas proceeds on almost the same types of active sites as it takes place for HDS. Unlike HDS sites, responsible for hydrogenolysis of CS bond, the MAS sites, responsible for alcohol formation, are modified by potassium (Fig. 1). 5 % K 10 % K 15 % K Fig. 1. TEM images of the CoMoS/Al 2 3 catalyst modified by 5, 10 and 15 % of K and the models of intercalation of K + ions between the layers of the MoS 2 crystallites. The TEM data witness that K addition increases stacking number. The catalytic examinations show that potassium promotes alcohol yield. Basing on these data we suppose that K ions intercalate between neighbouring MoS 2 layers affecting the active phase morphology and (AS) s selectivity in MAS. The Co-promoted catalyst is more selective to alcohols than the non-promoted one. Promoting activity Co in MAS and HDS lets us suppose that the nature of the active sites operating in both reactions is similar. [1] V.M. Kogan, P.A. ikulshin, Catal. Today 149 (2010) 224. [2] V.M. Kogan, P.A. ikulshin,.. Rozhdestvenskaya, Fuel 100 (2012) 2. [3] V.M. Kogan,.. Rozhdestvenskaya, I.K. Korshevets, Appl. Catal. A: Gen. 234 (2002)

179 P68 RELATISHIP BETWEE ACTIVE PHASE MRPHLGY AD CATALYTIC PRPERTIES F THE CARB-ALUMIA-SUPPRTED Co(i)Mo CATALYSTS I HDS AD HYD REACTIS P.A. ikulshin 1, V.A. Salnikov 1, A.A. Mozhaev 1, P.P. Minaev 1, V.M. Kogan 2, A.A. Pimerzin Samara State Technical University, Samara, Russia 2 -.D. Zelinsky Institute of rganic Chemistry, RAS, Laboratory of catalysis by trasition metals and their compounds, Moscow, Russia Effects of activated carbon of a carbon-coated alumina (CCA) support and active phase morphology of transition metal sulfide (TMS) catalysts in hydrotreatment (HDT) of S-containing compounds were studied. The catalysts were synthesized from Anderson-type heteropolycompounds and characterized with multiple methods: X-ray powder diffraction, 2 physisorption, temperatureprogrammed desorption of ammonia, pyridine-adsorbed Fourier transform infrared spectroscopy, H 2 temperature programmed reduction, and high resolution transmission electron microscopy. The catalysts were tested in hydrodesulfurization (HDS) of thiophene, dibenzothiophene and HDT of diesel. To interpret the obtained results, we used an interlayer dynamics concept developed recently [1]. The TPR measurements indicate hydrogen uptake by the C-coated support at reaction temperatures. It witnesses that CCA accumulates gas-phase hydrogen and could be a source of hydrogen for HDT reactions. Carbon affects active phase morphology: changing the carbon content it is possible to vary a stacking number/linear size ratio of the active phase particles and, thereby, to control hydrogenation to direct desulfurization (HYD/DDS) selectivity (Fig. 1). TF 10 (s Var2 Average stacking number 4 1 ) 3 Average length, nm L (a) Var3 S HYD/DS В L Var1 Average length, nm (b) 3 Average stacking number Fig. 1. 3D dependences of TF number (a) and HYD/DDS selectivity (b) in DBT HDS on average length and average stacking number of Co(i)MoS 2 particles in the catalysts; schematic visualization of the morphology of promoted MoS 2 slabs variation depending on the number of the active sites on the edges and rims of the slabs (c). An increase in the average linear size of the slab leads to a drop of HDS and HYD activities. The longer layers in the slabs, the fewer solid angles are, and so the higher the effect of the support. n the contrary, in the multilayered structure the support effect diminishes. The observed high HYD/DDS selectivity of the catalysts synthesized from AHM and nickel nitrate may be caused by low edge surface i on the MoS 2 slab which should also form the unpromoted Mo-sites responsible for the HYD reactions on the edges. The results suggest that the catalytic activity in HDS and HYD reactions depends on the shape of crystallites of the active phase. The results are interpreted using recently proposed concepts of interlayer dynamics. These concepts are helpful in establishing structure-activity relations for TMS. 1. V.M. Kogan, P.A. ikulshin,.. Rozhdestvenskaya, Fuel 100 (2012) (c)

180 P69 GEESIS F HDT CATALYSTS PREPARED WITH THE USE F Co 2 Mo 10 HPA AD CBALT CITRATE: STUDY F THEIR GAS AD LIQUID PHASE SULFIDATI P.A. ikulshin 1, A.V. Mozhaev 1, K.I. Maslakov 2, A.A. Pimerzin 1, V.M. Kogan Samara State Technical University, Samara, Russia 2 - M.V. Lomonosov Moscow State University, Chemistry Department, Moscow, Russia 3 -.D. Zelinsky Institute of rganic Chemistry, RAS, Laboratory of catalysis by trasition metals and their compounds, Moscow, Russia Production of clean fuels with less than 10 ppm sulfur content is one of the most important and claiming the attention problem in recent petroleum refinery. The countermeasures for the ultra deep desulfurization are to apply novel highly active catalysts, and to optimize the operation condition of the hydrodesulfurization (HDS) process. The development and application of more active and stable catalysts could enhance the productivity and improve the product quality without negative impacts on capital investment. Genesis of alumina supported hydrotreating (HDT) catalysts prepared with the use of decamolybdodicobaltate heteropolyanion (Co 2 Mo 10 HPA) and cobalt citrate during their sulfidation processes and deactivation in diesel HDT has been investigated. The sulfidation stage was studied for two procedures: gas phase sulfidation by H 2 S/H 2 and liquid phase treatment by a mixture of dimethyldisulfide in diesel at various temperatures and durations. The catalysts have been studied by 2 adsorption, thermogravimetric analysis, X-ray photoelectron spectroscopy and highresolution transmission electron microscopy methods. The catalysts were tested in HDT of mixture of 70 wt.% straight run gas oil with 16 wt.% light cycle oil and 14 wt.% light coker gas oil. Mechanisms of the active phase formation in the course of gas and liquid phase sulfidation processes have been established (Fig. 1). Fig. 1. CoMoS phase formation mechanisms during gas and liquid phase sulfidation of the Co 3 (CA) Co 2 Mo 10 /Al 2 3 catalyst (S average stacking number, L average length were found from TEM; Co content in CoMoS phase and (Co/Mo) slab were found by XPS). It was found that gas phase sulfidation led to formation of the CoMoS active phase with higher cobalt content comparing to liquid sulfidation of the catalyst and initial activity of the gas phase treated catalysts in diesel HDT was also higher than catalysts subjected to liquid sulfidation. Catalytic examination after accelerated deactivation conditions showed that the liquid phase sulfided sample was more resistant to the deactivation. Probably it is due to stabilization of active phase particles by coke formed intensively during liquid phase sulfidation. In liquid phase sulfidation, both metals are sulfided simultaneously with the formation of nuclei of CoMoS phase II type at low temperature (230 0 C). At high temperature (340 0 C) the increase of particle size of CoMoS phase is occurred. 180

181 P70 SYTHESIS F HEPTASACCHARIDE FRAGMET CRRESPDIG T α-(1-3)-gluca F ASPERGILLUS FUMIGATUS M.V. rekhova, B.S. Komarova,.E. ifantiev Laboratory of Glycoconjugate Chemistry,.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences Leninsky Prospect 47, Moscow, Russia For immunocompromised individuals Aspergillus fumigatus is the most important and life threatening pathogen. [1] In the cell walls of this ubiquitous fungus -(1 3)-glucan constitutes the main polysaccharide, [2] which forms biofilms and is a cause of permanent infection. [3] Previously a synthesis of spacer armed -(1 3)-pentaglucoside conjugates with BSA and biotin was achieved. These derivatives were used for obtaining and characterization of antibodies recognizing α-(1 3)- glucan, which were used for tracing A. fumigatus cells. However for the final goal of the project, the development of a vaccine against A. fumigatus, the five glucosyl units in the chain is not enough. In the present report a synthesis of 3-aminopropyl -(1 3)-pentaglucoside 1 (Scheme) is described. The success of convergent scheme toward the target compound relied on the use of disaccharide 2 which was modified by orthogonal levulinoyl (Lev) and p-methoxyphenyl (pmp) groups. The ability to remove Lev and pmp groups independently made it possible to prepare disaccharide donor 5 and acceptor 3 from one precursor and then to combine them to get tetrasaccharide 6. Glucosylation of the trisaccharide acceptor 9 with tetrasaccharide donor 8 proceeded smoothly to give heptasaccharide backbone. Stereoselectivity of each -glucosylation of the whole scheme was controlled by -stereodirecting benzoyl group at -6. [4] While high yields of all glucosylations were attained due to the choice of -phenyl-trifluoracetidoyl leaving group and MeTf as a promoter. [5] Free heptasaccharide 1 was converted to BSA and biotin conjugates using amino group of the spacer. 1. A. Gastebois; C. Clavaud; V. Aimanianda; J. P. Latgé Future Microbiology 2009, 4, D. Maubon; S. Park; M. Tanguy; M. Huerre; C. Schmitt; M. C. Prévost; D. S. Perlin; J. P. Latgé; A. Beauvais Fungal Genetics and Biology 2006, 43, A. Beauvais; C. Schmidt; S. Guadagnini; P. Roux; E. Perret; C. Henry; S. Paris; A. Mallet; M. C. Prévost; J. P. Latgé Cellular Microbiology 2007, 9, B. S. Komarova; M. V. rekhova; Y. E. Tsvetkov;. E. ifantiev Carbohydrate Research 2014, 384, B. S. Komarova; Y. E. Tsvetkov; Y. A. Knirel; U. Zähringer; G. B. Pier;. E. ifantiev Tetrahedron Letters 2006, 47,

182 P71 SUPRAMLECULAR STRUCTURES I ADDUCTS F CYMATREECARBXYLIC ACID WITH FIVE- AD SIX-MEMBERED ARMATIC -BASES P.S. Koroteev, A.B. Ilyukhin, Zh.V. Dobrokhotova, V.M. ovotortsev. S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences ne of the goals of supramolecular chemistry is the search for new molecules that are potentially capable of self-assembly owing to nonvalent interactions. The molecule of cyclopentadienyltricarbonylmanganese (η 5 -C 5 H 5 )Mn(C) 3 (cymantrene), which has the piano stool shape, besides of many other peculiarities, has specific properties as a potential building block for supramolecular architectures both due to its special geometry and the nature of its constituent moieties. Earlier we have studied the crystal-chemical behavior of anions of cymantrenecarboxylic acid (η 5 -C 5 H 4 CH)Mn(C) 3 (HL) and more sterically hindered β- cymantrenoylpropionic acid (η 5 -C 5 H 4 C(CH 2 ) 2 CH)Mn(C) 3 combined with alkaline metals cations and with protonated molecules of polytopic nitrogen bases, which have various geometries and provide opportunities for supramolecular interactions [1]. ew derivatives of HL and polytopic aromatic -bases: imidazole (I), pyrazole (II), 3-amino-1,2,4- triazole (III), 4-amino-1,2,4-triazole (IV), 2-aminopyridine (V), 3-aminopyridine (VI), 4- aminopyridine (VII), 2,4-diamino-6-hydroxypyrymidine (VIII) were obtained and characterized by X-ray diffraction. It has been shown that two- and three-dimensional supramolecular structures of these derivatives are formed owing to special properties of the cymantrene moiety, in particular its ability to form C H hydrogen bonds (HBs), but the type of the structure is mostly determined by the geometry of the cation and by its capability of HBs formation (Fig.1). The possibility of organic molecules of various nature to self-organize due to protonation and/or HBs formation and with regard to specific geometries is discussed. Fig 1. Fragments of the structures of VII HL (left) and VIII HL (right). [1] A.B. Ilyukhin, P.S. Koroteev, M.A. Kiskin, Zh.V. Dobrokhotova, V.M. ovotortsev, Journal of Molecular Structure, 1033 (2013) Acknowledgements: This study was financially supported by the RFBR (o , ), the Council on Grants of the President of the RF (Sh ) and the Presidium of the Russian Academy of Sciences. 182

183 P72 UCLEFILIC BRM- AD IDDIFLURMETHYLATI F ALDEHYDES M.D. Kosobokov, V.V. Levin, M.I. Struchkova, A.D. Dilman IC RAS, Moscow, Russia owadays, Ruppert Prakash reagent (Me 3 SiCF 3 ) 1 and its functionalized analogues 2, 3 are widely applicable fluorinated reagents in organic synthesis. Indeed, these air stable silanes are convenient agents for nucleophilic fluoroalkylation reactions. They exhibit their nucleophilic reactivity under silaphilic Lewis base activation, generating a pentacoordinate intermediate, which could react with a suitable electrophile (e.g., aldehydes). Reactions of the Ruppert Prakash reagent (X =F) and chloro-substituted analog (X = Cl), as well as many other functionalized silanes, follow this pathway. However, reactions of a bromo-substituted silane (X = Br) with aldehydes mediated by a fluoride ion have been unsuccessful, presumably owing to facile decomposition of anionic intermediate to difluorocarbene. Indeed, silane Me 3 SiCF 2 Br can generate difluorocarbene even in the presence of weak Lewis bases such as chloride and bromide ions. While (bromodifluoromethyl)trimethylsilane (1a) can be readily obtained from the Ruppert Prakash reagent, iodinated silane (1b) has not been known. We prepared silane 1b from silane 1a in 70% yield by the bromine/zinc exchange followed by iodination. Then, we developed a method for nucleophilic bromo- and iododifluoromethylation of aldehydes using bromo- and iodo-substituted difluoromethyl silicon reagents (Me 3 SiCF 2 X). The reaction is performed in the presence of a combination of tetrabutylammonium and lithium salts Bu 4 X/LiX (X = Br or I) in propionitrile. 4 It is believed that, in this process, a short-lived halodifluoromethyl carbanion serves as nucleophile, which is reversibly generated from difluorocarbene and a halide anion. This work was supported by the Russian Science Foundation (project ). [1] Liu, X.; Xu, C.; Wang, M.; Liu, Q. Chem. Rev ASAP, doi: /cr400473a [2] Kosobokov, M. D.; Dilman, A. D.; Struchkova, M. I.; Belyakov, P. A.; Hu, J. J. rg. Chem. 2012, 77, [3] Kosobokov, M. D.; Dilman, A. D.; Levin, V. V.; Struchkova, M. I. J. rg. Chem. 2012, 77, [4] Kosobokov M. D., Levin V. V., Struchkova M. I., Dilman A. D. rg. Lett. 2014, 16,

184 P73 EW REGISELECTIVE RUTE T 5-CARBXY-1,2,3-TRIAZLES VIA PALLADIUM-CATALYZED CARBYLATI F 5-ID-1,2,3- TRIAZLES Y.. Kotovshchikov, G.V. Latyshev,.V. Lukashev, I.P. Beletskaya Chemistry Department, Lomonosov Moscow State University, Moscow, Russia Various compounds containing 1,2,3-triazole moiety are of great importance in coordination and supramolecular chemistry, medicine, polymer and materials sciences [1]. In particular, some 5- carboxy-1,2,3-triazoles were shown to be kinases inhibitors as well as to exhibit antiviral and antibacterial effects [2]. So far, the only synthetic route to these compounds was thermal [3+2]- cycloaddition of organic azides to propiolic acid derivatives. The main drawback of the method is low regioselectivity. Formation of two regoisomers diminishes yields of desired 5-carboxy-1,2,3- triazoles and complicates isolation of the products. Since 5-iodo-1,2,3-triazoles can be prepared from 1-iodoalkynes and azides under Cu(I) catalysis [3], the subsequent carbonylation reaction could became a new regioselective approach to 5-carboxy-1,2,3-triazoles. We have shown that alkoxycarbonylation of 5-iodo-1,2,3-triazoles could be performed under mild reaction conditions with 1 atm of C in the presence of 5 % Pd(Ac) 2. Various functional groups (ester, hydroxyl, ketone, nitro) were tolerated and a number of 5-methoxycarbonyl-1,2,3-triazoles were obtained in good to excellent yields. The transformation appeared sensitive to steric effects, and bulky substituents led to decrease in reaction rate and/or yield. This work was supported by RFBR (grant а). 1. (a) M. Meldal, C. W. Tornøe. Chem. Rev. 2008, 108, 2952; (b) J. E. Hein, V. V. Fokin. Chem. Soc. Rev. 2010, 39, (a) H. Cheng, J. Wan, M.-I. Lin, Y. Liu, X. Lu, J. Liu, Y. Xu, J. Chen, Z. Tu, Y.-S. E. Cheng, K. Ding. J. Med. Chem. 2012, 55, 2144; (b) G. S. Gadaginamath, M. G. Bhovi. Indian J. Chem., Sect. B: rg. Chem. Incl. Med. Chem. 2005, 44, J. E. Hein, J. C. Tripp, L. B. Krasnova, K. B. Sharpless, V. V. Fokin. Angew. Chem., Int. Ed. 2009, 48,

185 P74 A GEERAL APPRACH T THE SYTHESIS F THIPHEE- CTAIIG ELECTR-DR AD -ACCEPTR FRAGMETS FR CJUGATED PLYMERS FR SLAR PHTVLTAIC CELLS I.. Konstantinov 1, M.M. Krayushkin 1, M.L. Keshtov 2, S.A. Kuklin 2, V.S. Kochurov 3,.A. Radychev 4, A.R. Khokhlov D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - A.. esmeyanov Institute of rganoelement Compounds RAS, Moscow, Russia 3 - M.V. Lomonosov Moscow State University, Physical Department, Moscow, Russia 4 - Carl von ssietzky University of ldenburg, Physical Department, ldenburg, Germany The goal of this work was developing a general method for creating both electron-donor, and electron-acceptor moieties in terms of dithienylethenes to use them for preparation of new conjugated polymers as an electroactive material for solar cells. Bis(trimethylstannyl)-2-dodecylbenzotrithiophene monomer (1) as a donor in D A copolymers was synthesized for the first time from the corresponding dithienylethene with thiophene bridge [1]. C 1 7 H 3 5 C 1 2 H 2 5 S R H 3 1 C 1 5 R 1 S C 8 H 1 7 S S S S Br S 2 S Br Sn 1 Sn * S C 1 2 H 2 5 P S S Br 3.R = Ar * n S S Dibromides 2-6 were synthesized also analogously from dihetarylethenes [1,2] and used as monomers of the electron-acceptor nature. ew narrow-band conjugated polymers of type P with a rigid alternation of donor and acceptor units were prepared on the basis of these monomers, under the Stille reaction conditions in the presence of tetrakis(triphenylphosphine)palladium as a catalyst [3,4]. The thermal, optical, electrochemical, and photovoltaic properties of the copolymers were studied [5]. 1. M.M. Krayushkin and M.A. Kalik, Syntheses of Photochromic Dihetarylethenes. In: Katritzky, editors: Advances in Heterocyclic Chemistry, Vol. 103, xford: Academic Press; 2011, p Shirinian, V.Z., Lonshakov, D.V., Kachala, V.V., Zavarzin, I.V., Shimkin, A.A., Lvov, A.G., and Krayushkin, M.M., J. rg. Chem., 2012, vol. 77, p Keshtov, M.L., Marochkin, D.V., Kochurov, V.S., Komarov, P.V., Parashchuk, D.Yu., Trukhanov, V.A., and Khokhlov, A.R., Vysokomol. Soedin., Ser. B., 2014, vol. 56, no. 1, p Keshtov, M.L., Toppare, L., Marochkin, D.V., Kochurov, V.S., Parashchuk, D.Yu., Trukhanov, V.A., and Khokhlov, A.R., Vysokomol. Soedin., Ser. B., 2013, vol. 55, no. 6, p M.L. Keshtov, S.A. Kuklin, V.S. Kochurov, I.. Konstantinov, M.M. Krayushkin,.A. Radychev, and A.R. Khokhlov, Doklady Chemistry, 2014, Vol. 454, Part 2, pp Br E t B u Br S 4 S Br Br 5.R 1 = 6.R 1 = S S S Br C 1 0 H 2 3 C 8 H 1 7 C 1 0 H 2 3 C 8 H 1 7

186 P75 PHTCHEMICAL REARRAGEMET F CHRMES AD BEZFURAS K.S. Chudov 1, K.S. Levchenko 1, V.. Yarovenko 1, M.M. Krayushkin 1,.I. Kobeleva 2, T.M. Valova 2, V.A. Barachevsky 2, E.P. Grebennikov D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - Photochemistry Center, Russian Academy of Sciences, Moscow, Russia At present optical information recording in the existing Ds is based on thermoinduced transformation processes of substances that change the reflection properties under the action of light. Prospects for increasing the information capacity of Ds are related to the development of multilayered photosensitive detection media based on organic compounds that being irradiated undergo irreversible photochemical transformations of the initial non-fluorescing compounds into fluorescent photoproducts. It has recently been shown that UV-irradiated acylchromones I that do not manifest fluorescence are irreversible rearranged to fluorescent furano[3,4-b]chromenones II. Based on the latter, we are developing multilayered detection media for Ds of the WRM archive type [1,2]. R R U V R 2 R 2 R 1 I R, R 1, R 2 = H, F G, A r, H e ta r We synthesized a set of benzofurans IV with a highlighted furylpropenonic fragment and demonstrated that they under UV-illumination also transformed into tricondensed derivatives V, that is the photorearrangement by all appearances has a common character. It is worthy noted that initial compounds IV did not possess fluorescence whereas the products V did. R 1 III R 1 = M e, B r H B rc H 2 C R 2 R 1 R 2 II R 1 R 1 = M e, B r; R 2 = P h, A r The fluorescence properties of the compounds due to irreversible photochemical transformations of chromones and benzofurans in toluene were studied. The quantum yields of the photoproducts were measured. Some relationships between the fluorescence properties of the photoproducts and their structure were revealed. A part of the compounds are characterized by a high Stokes shift and other profitable properties that provide their practical application in photosensitive detection media with nondestructive fluorescence reading optical information. 1. V.A. Barachevsky,.I. Kobeleva, T.M. Valova, A.. Ait, A.A. Dunaev, A.M. Gorelik, M.M. Krayushkin, K.S. Levchenko, V.. Yarovenko, V.V. Kyiko, E.P. Grebennikov, pt. Mem. & eur. etworks; 19 (2010), V.A. Barachevsky, M.M. Krayushkin, V.V. Kyiko, E.P. Grebennikov, Phys. Status Solidi C, 8 (2011), IV UV R 1 V R 2 186

187 P76 EW CHRME-CTAIIG LIGADS K.A. Myannik 1, V.. Yarovenko 1, K.S. Levchenko 2, M.M. Krayushkin D. Zelinsky Institute of rganic Chemistry, RAS, Moscow, Russia 2 - Central Research Technological Institute Tekhnomash", Moscow, Russia Chromone derivatives are of doubtless interest as bioactive compounds and elements of detecting media for multilayer optical discs of superhigh capacity. We showed the possibility to synthesize chromone-containing ligands containing fragments of thiohydrazides of oxaminic acids 1-9. F S F S H H F H S H F S H H C E t F S S H H S H H H S H C E t H H 2 F H 2 6 S S H H S H H S H H C E t H H H H

188 P77 EW CMPLEX STRUCTURES BASED XAMIIC ACID THIHYDRAZIDES M.M. Krayushkin, V.. Yarovenko, I.V. Zavarzin.D. Zelinsky Institute of rganic Chemistry, RAS, Moscow, Russia It is known that among thiohydrazides there are many drugs of different action, which is enhanced, in many cases, in the presence of metal cations. We showed a possibility to synthesize complexes from the ligands containing fragments of oxaminic acid thiohydrazides The geometric parameters of synthesized complex 1 were studied by X-ray diffraction analysis (Fig. 1). Fig. 1 Fig. 2 The square-planar coordination mode of nickel is attained due to two additional atoms: S i with a distance of 3.407(2) Å and ii with a distance of 3.451(4) Å (symmetry transform i: x, y+1, z and i: x, y-1, z ) with the formation of a distorted octahedron around the nickel atom. An infinite chain is thus formed (Fig. 2). 188

189 P78 THREE-CMPET CDESATI F IMIAZLIDIES WITH ALDEHYDES AD MELDRUM`S ACID. SYTHESIS AD STUDY F PRPERTIES F THE IMIDAZPYRIDIE-2,5-DIES K.S. Krylov, A.. Komogorttsev, B.V. Lichitsky, A.A. Dudinov, M.M. Krayushkin.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia Multicomponent reactions are indispensable tools which are used for the construction of different heterocyclic systems. The marked advantage of such a reactions are the versatility and efficiency of synthesis of the new organic materials. The diversity of the multicomponent reactions allows to create a broad set of compounds without using the methodology of the complicated multistage synthesis. The present work devoted to the development of our previously elaborated method, based on multicomponent reaction of the heterocyclic enamines, carbonyl compounds and the Meldrum`s acid. We have proposed the versatile method of preparation of the previously unknown 7-aryl-1- phenyl-1,6,7,7-tetrahydro-4h-imidazo[4,5-b]pyridine-2,5-diones 1 based on the three component condensation of iminoazolidines 2, aldehydes 3 and the Meldrum`s acid 4. H H P h + Ar C H + Et H H Ar P h The properties of the obtained imidazopyridine-2,5-diones 1 were investigated. It is demonstrated that compounds of type 1 undergo the acid hydrolysis with formation of previously unknown 5- substituted 1-phenylimidazolidine-2,4-diones 5. H Ar P h A c H H 2 Ar H P h 1 5 References 1. B. V. Lichitsky, R. M. Belyi, A.. Komogortsev, A. A. Dudinov, M. M. Krayushkin, Russ. Chem. Bull., Int. Ed., 2013, 62,

190 P79 RADICAL CRSS-DEHYDRGEATIVE C- CUPLIG F 1,3- DICARBYL CMPUDS WITH HYDRXYLAMIE DERIVATIVES I.B. Krylov, A.. Terent`ev, B.. Shelimov, G.I. ikishin.d. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation Cross-dehydrogenative coupling, as a rule, is a reaction, in which two different starting molecules are connected by a new bond with the elimination of one hydrogen atom from each of the molecules. In the last decade, these reactions have attracted great attention because they can be used to form a new bond with almost the maximum possible atom economy and do not require additional synthetic steps for the introduction of functional groups (Hal, Tf, BR 2, SiR 3, SnR 3, ZnHal, etc.) that are necessary in other approaches to the cross-coupling. The cross-dehydrogenative С-С coupling was studied in most detail; the C-, C-P and C- crosscoupling reactions are less well developed. It is difficult to achieve high selectivity in the oxidative C- coupling because the starting compounds are prone to side oxidation and fragmentation reactions giving, for example, alcohols and carbonyl compounds. In the present work, the cross-dehydrogenative С coupling of β-dicarbonyl compounds with oximes, [1] -hydroxyimides [2] and -hydroxyamides [2] was performed for the first time. The reaction proceeds in the presence of the different metal-containing oxidants: KMn 4, Mn(Ac) 2 /KMn 4, Co(Ac) 2 /KMn 4, Mn(Ac) 3 2H 2, Mn 2, Mn(acac) 3, Fe(Cl 4 ) 3, Cu(Cl 4 ) 2 6H 2, Cu( 3 ) 2 2.5H 2, and (H 4 ) 2 Ce( 3 ) 6 ; yields are 27 94%. The synthesis can be easily scaled up to gram quantities of the target products. The method is applicable for a wide variety of β-diketones and β-keto esters; 2-substituted malonic esters and heteroanalogues of β-dicarbonyl compounds, 2-substituted malononitriles and cyanoacetic esters, are substantially less reactive in the cross-dehydrogenative coupling with tested hydroxylamine derivatives. Apparently, the oxidant serves two functions in the cross-dehydrogenative coupling reaction: the generation of -oxyl radicals from hydroxylamine derivatives and the one-electron oxidation of β-dicarbonyl compounds. The formation of -oxyl radicals was confirmed by ESR spectroscopy. Acknowledgements. This work was supported by the Russian foundation for Basic Research (Grant ). 1. I. B. Krylov, A.. Terent ev, V. P. Timofeev, B.. Shelimov, R. A. ovikov, V. M. Merkulova, G. I. ikishin, Iminoxyl Radical-Based Strategy for Intermolecular C- Bond Formation: Cross-Dehydrogenative Coupling of 1,3-Dicarbonyl Compounds with ximes // Adv. Synth. Catal., 2014, 356, DI: /adsc A.. Terent ev, I. B. Krylov, V. P. Timofeev, Z. A. Starikova, V. M. Merkulova, A. I. Ilovaisky, G. I. ikishin, xidative C- Cross-Coupling of 1,3-Dicarbonyl Compounds and Their Heteroanalogues with -Substituted Hydroxamic Acids and -Hydroxyimides // Adv. Synth. Catal. 2013, 355, DI: /adsc

191 P80 THE FIRST EATISELECTIVE RGACATALYTIC REACTI I SUPERCRITICAL CARB DIXIDE: ASYMMETRIC MICHAEL ADDITI F DIPHEYLPHSPHITE T α-itralkees E.V. Kryuchkova, I.V. Kuchurov, A.G. igmatov, A.S. Kucherenko, S.G. Zlotin.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky prospekt, 47, Moscow, Russia Recently, we discovered [1] that asymmetric organocatalytic reactions can be efficiently carried out in liquid carbon dioxide. We have expected that the use of C 2 in the supercritical state (sc-c 2 ) as a reaction medium may be even more promising as it is characterized by higher diffusion rates and a unique capability of dispersing poorly soluble reagents, thus enhancing the reaction scope, rates and selectivity. Herein we report that α-nitroalkenes 2 enantioselectively accept diphenylphosphite (1) in sc-c 2 in the presence of bifunctional tertiary amines 4 and 5 (5 mol %)) bearing the squaramide fragment to afford corresponding β-nitrophosphonates 3 in high yields and with enantiomeric access of up to 94% ee [2]. In this way enantiomeric β-nitrophosphonates 3 and ent-3, which are precursors of optical antipodes of β-amino phosphonic acid derivatives that occur in nature and possess valuable biological activities, were synthesized. Furthermore, we disclosed a significant potential of sc-c 2 for the fractional extraction of products and recovery of precious chiral catalyst. The obtained results contribute to green chemistry as they eliminate toxic organic solvents originated from exhausting hydrocarbon resources and facilitate separation and purification steps that usually have the highest environmental impact in chemical processes. References 1. A.G. igmatov, I.V. Kuchurov, D.E. Siyutkin, S.G. Zlotin, Tetrahedron Lett. 2012, 53, I.V. Kuchurov, A.G. igmatov, E.V. Kryuchkova, A.A. Kostenko, A.S. Kucherenko, S.G. Zlotin, Green Chem. 2014, 16,

192 P81 SYTHESIS F EW CLASS F RGAIC PERXIDES: IDPERXIACETALS, BY TREATMET F ELE ETHERS WITH IDIE-HYDRPERXIDE SYSTEM A.. Kulakova, A.T. Zdvizhkov, A.. Terentev, R.A. ovikov, G.I. ikishin. D. Zelinsky institute of organic chemistry, Laboratory for Studies of Homolytic Reactions, Moscow, Russia rganic peroxides are very common for development of antitumor and antiparasitic drugs. However, effectiveness of drugs reduces due to the mobilization of cells defense mechanisms with respect to specific substances. This problem is solved by the development of new classes of biological compounds, as well as their chemical modifications. In the present work, we studied the interaction of mono-and bicyclic enol ethers with a system of I 2, hydroperoxide. This system allows getting number of new peroxide compounds containing an iodine atom, which makes possible further modification of the peroxide molecule. Commercially available monocyclic enole esters of 2,3-dihydrofuran and 3,4-dihydro-2H-pyran were selected as starting materials, as well as their bicyclic analogs that can be synthesized by a known method. Firstly, we studied the interaction of monocyclic enol ethers with the system, I 2 -ButH (TBHP) and I 2 -tetrahydropyranyl hydroperoxide (THPHP). We have proposed a method to obtain iodoperoxide with yields up to 90%. The reaction is carried out in diethyl ether at 0 C in the presence of 4-fold excess hydroperoxide and an equivalent amount of iodine. Having developed iodoperoxidation method, we investigated the reaction of the bicyclic enole ethers with the I 2 -H 2 2 system. Iodoperoxides were obtained with yield of 80%. The reaction was carried under the action of iodperoxidation monocyclic enole ethers at - 40 C. When using a more bulky t-buh were obtained addition products the peroxide to double bond not containing iodine atom. In the case of THPHP reaction did not proceed at all. In this work the methodology of synthesis of a new class of organic peroxides - vicinal iodperoxyacetals and ketals based on mono-and bicyclic enole ethers was developed. These compounds may be useful for inventing new anticancer and antiparasitic drugs. Acknowledgements This work was supported by the Russian Science Foundation (Grant ). 192

193 P82 APPLICATI F AZA-CPE-MAICH REACTI FR HIGHLY EFFICIET STERSELECTIVE SYTHESIS F DERIVATIVES F (2SR, 3ASR, 8ASR)-3A-METHYLCTAHYDRCYCLHEPTA[B]PYRRL- 4(1H)-E I.. Myasnyanko, E.R. Lukyanenko, A.V. Kurkin M.V. Lomonosov Moscow State University Saturated heterocyclic compounds are much more attractive objects for the development of new drugs compared to traditionally used in medicinal chemistry heteroaromatic compounds, since they, as a rule, possess better solubility, pharmacokinetic properties and bioavalability [1, 2]. In this regard, development of efficient stereoselctive methods for the syntheis of such compounds (having patent purity) is an important task for scientists working in drug discovery field. Earlier, we developed highly efficient steroselective synthesis of cis- and trans-fused 3-substituted octahydrocyclohepta[b]pyrrol-4(1h)-ones using aza-cope-mannich reaction as a key step [3, 4]. In the presnt work we present simple highly efficient steroselective synthesis of 2-substituted cis-fused octahydrocyclohepta[b]pyrrol-4(1h)-ones starting from cheap cyclohexene oxide using tandem of aza-cope and Mannich reactions as a key step. Amino ketones 1 were obtained as sole stereoisomers in high overall yield, their structures were confirmed by X-ray (for R = Ph and i-pr). This work was supported by Russian Foundation for Basic Research (projects , , ). 1. Ritchie, T. J., Macdonald S. J. F., Young, R. J., Pickett S. D. Drug Discov. Today 2011, 16, Meanwell,. A. Chem. Res. Toxicol. 2011, 24, Belov, D. S., Lukyanenko, E. R., Kurkin, A. V., Yurovskaya, M. A. Tetrahedron 2011, 67, Belov, D. S., Lukyanenko, E. R., Kurkin, A. V., Yurovskaya, M. A. J. rg. Chem. 2012, 77,

194 P83 SYTHESIS AD TRASFRMATIS DERIVATIVES F AMI ACID CTAIIG ITRGEUS HETERCYCLE D.R. Latypova 1, V.A. Dokichev 1, Yu.V. Vahitova Institute of rganic Chemistry Ufa SC RAS 2 - Institute of Biochemistry and Genetics Ufa SC RAS The achievements of modern pharmacology and clinical medicine are largely determined by the synthesis of new groups of physiologically active compounds. Compounds containing amino acid, pyrrolidone and hexahydropyrimidine moieties are natural and important group of biologically active compounds. A lot of them have a variety of pharmacological effects (anti-tumor, antiplatelet, anti-bacterial and anti-arrhythmic, etc.). In order to develop effective regio- and stereoselective methods of synthesis of the biologically active amino acids derivatives containing nitrogen heterocycle studied the interaction of CH-acids (acetone, benzyl acetone, ethyl acetoacetate and 1,3-acetonedicarboxylic acid diethyl ester) with formaldehyde, primary amines and amino acids in the Mannich reaction conditions. n the basis of the synthesized 1,3-hexahydropyrimidines containing in the 5-position the acetyl and the ester group 5-methyl-2,4-dihydro-3H-pyrazol-3-ones with amino acid moieties are obtained. It has been established that the splitting of 1,3- hexahydropyrimidine cycle with hydrazine hydrate which follow with retention of configuration of the optically active centers. 3-Diazopyrrolidin-2-ones that are of interest as structural fragments for production analogies of γ- aminobutyric acid - the chief inhibitory neurotransmitter in the mammalian central nervous system are synthesized. A method of obtaining inaccessible heterocyclic compounds containing a pyrazolo[1,5-c]pyrimidine moiety based on the van Alphen-Huettel rearrangement of products of 1,3-dipolar cycloaddition 3-diazo-4-phenylpyrrolidone with dimethyl acetylenedicarboxylate and 5-diazo-exo-3-azatricyclo[ ,6 ]decan-4-one with quinone is proposed. Among the investigated groups of substances novel compounds that have cytotoxic properties against both cell HEK293 and SH-SY-5Y are discovered. 194

195 P84 METAL/PLYMER ACATALYSTS FR HYDRGE-XYGE MICR-PWER EERGY SURCES M.V. Lebedeva 1,.A. Yashtulov 2,.E. Minina 1, K.S. Smirnov 2, S.S. Gavrin Lomonosov Moscow state university of fine chemical technologies, Moscow, Russia 2 - ational research university "Moscow power engineering institute", Moscow, Russia Development of highly active and stable nanoelectrocatalysts for micro-power energy sources (MPES) on the basis of fuels conversion is one of the fundamental problems of modern science and energy. The modification of solid polymer membranes (SPM) by metal nanoparticles of not only the surface but also the volume is used to create efficient catalytically active, stable and cheap materials for energy sources of new generation. The introduction of inorganic components makes it possible to enhance the exploitation characteristics of the solid polymer membranes [1-3]. At present time the most relevant and promising energy sources are fuel cells with solid polymer electrolyte (SPE) due to their extensive use in stationary applications and mobile electronic equipment. Electrolyte in such system is proton exchange perfluorinated polymer with ionogenic sulfo groups ( S 3 H) of the afion type (Du Pont) that provides unipolar conductivity on hydrogen ions [1,2]. As nanostructured matrix-substrate in our work it was used the afion type solid polymer membrane (SPM) with a thickness of less than 0.2 mm. The modification by one-component and bimetallic nanoparticles of platinum and base metal of the SPM surface and volume promotes additional catalytic oxidation of hydrogen-containing fuels (H 2, C 2 H 5 H, HCH, CH 3 H and others). Due to introduction of nano-sized metal in the polymer matrix and application of bimetallic systems there is an increasing of the catalytic and functional activity of metal-polymer nanocomposites and reduced the consumption of expensive Pt and Pd catalysts [1,2]. The aim of the present study was to establish the influence of the metal/polymers Pt/f and Pd/f synthesis parameters on the catalytic activity of platinum nanoparticles in the hydrogen oxidation and oxygen reduction reactions. The platinum metal nanoparticles solutions were prepared by the radiation chemical reduction 60 Co in reverse micelle solutions [1,2]. By varying the synthesis conditions one can control the nanoparticles size, content and functional properties. By means of the modern physico-chemical research methods, as electron microscopy, x-ray phase analysis, cyclic voltammetry it was performed the investigation of nanoparticle and nanocomposite functional properties. It was found that when reducing the size of metal nanoparticles (less than 8 nm) catalytic activity of metal/polymer nanocomposites (current density, catalytically active surface area) increases [1,2]. The work was supported by RFBR (grant ofi_m2). References [1] Yashtulov.A., Flid V.R. Russ. Chem. Bull V Р [2] Yashtulov.A., Revina A.A., Lebedeva M.V., Flid V.R. Kinetics and catalysis V P [3] Limpattayanate S., Hunsom M. Renewable Energy V P

196 P85 TRÖGER BASE AS A SIGLE SURCE F CHIRALITY I A EW BIS(SALICYLALDIMIAT) CATALYST FR RIG-PEIG F PRPYLEE XIDE D.A. Lenev 1, R.G. Kalinin 1, V.A. Kardash 1, A.V. Kiselyova 1, I.. Konstantinov IST LLC, Tomsk, Kuzovlevskii trakt 2, str Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, Moscow Recently many privileged catalysts, variations of C 2 -symmetric Schiff base salen ligands of Jacobsen and Katsuki, modified by pendant ammonium arms with nucleophilic counterions, and corresponding cobalt catalysts have been developed.[1][2][3] They have been intensively used in the popular field of stereoregular co-polymerization of alkene oxides with carbon dioxide to yield regular polymers polyalkene carbonates, such as polypropylene carbonate PPC or polycyclohexene carbonate PCHC. Stereotacticity and stereointegrity of PCHC influences its crystallinity, melting point and thermal stability, which is higher in the case of stereocomplex polymeric racemate.[1] Co-polymerization of (rac)-propylene oxide with C 2 yields stereogradient racemic stereocomplex PPC with improved thermal stability, and thus, processability.[2] The PPC material has been commercialized and the molecular formulas of the respective catalysts have been patented heavily.[3] Tröger base (TB)[4] could represent valuable asset for its practical use in asymmetric catalysis. In order to rely upon TB not only as fascinating, but also as privileged structure, we followed an algorithm in building a molecule with a single C 2 axis for the single TB diamine and single salen core, aligning sequentially the carbon of C bridge, the metal ion, and the center of ()CC() bond of unsubstituted 1,2-ethylenediamine. In this preliminary report we present an approach to the synthesis of the newly designed salen complex 1 with chirality solely due to asymmetric atoms of enantiopure TB, and we report the preparation of the system capable of efficient catalysis of cycloaddition of propylene oxide with C 2 to yield cyclic propylene carbonate with high T and TF X.-B. Lu, W.-M. Ren, G.-P. Wu, Acc. Chem. Res., 2012, 45, ; G.-P. Wu, W.-M. Ren, Y. Luo, B. Li, W.-Z. Zhang, X.-B. Lu, J. Am. Chem. Soc. 2012, 134, K. akano, S. Hashimoto, M. akamura, T. Kamada, K. ozaki, Angew. Chem. Int. Ed. 2011, ; B. Y. Lee, A. Cyriac, ature Chem., 2011, 3, A. Tullo, Capturing Carbon, in: Chem. Eng. ews, June 23, 2008, vol. 86(25), p.21; ovomer, Inc.: W 2011/ (S. D. Allen, A. E. Cherian, C. A. Simoneau, J. J. Farmer) 4. F. Vögtle, Fascinating molecules in rganic Chemistry, Wiley, Chichester, UK, 1992; B. Dolenský, M. Havlík, V.Král, Chem. Soc. Rev. 2012, 41,

197 P86 GEMIAL SILIC/ZIC REAGET AS A EQUIVALET F DIFLURMETHYLEE BIS-AI V.V. Levin, A.A. Zemtsov, M.D. Kosobokov, A.D. Dilman IC RAS, lab.8, Moscow, Russia Elaboration of new methods for the synthesis of fluoroorganic compounds is important owing to unique effect of fluorine atoms on their biological activity. Synthetic methods based on the introduction of fluorinated fragments into organic substrate are most widely presented. While various methods for the introduction of the CF 3 -group have been documented, approaches for the synthesis of compounds bearing CF 2 -fragment notably less abundant. At the same time this fragment is isosteric to ethereal oxygen, which makes compounds with this moiety highly attractive as promising pharmaceuticals. Typically, Synthesis of CF 2 -containing products involves deoxofluorination reaction or relies on building block approach. Also we recently described a strategy for assembling these compounds from difluorocarbene, nucleophile and electrophile 1. We present a germinal silicon/zinc binucleophilic reagent (1) for coupling with two electrophilic spesies 2. This reagent conveniently prepared by cobalt-catalyzed bromine/zinc exchange in Me 3 SiCF 2 Br using isopropylzinc iodide. Under the copper catalysis reagent 1 smoothly reacts with allylic halides with formation of fluorinated silanes 2. This silanes were employed as nucleophilic reagents with a range of aldehydes, provides after work-up the fluorinated alcohols 3. In this products both nucleophilic sites of initial reagent 1 successively replaced by two electrophiles. Acknowledgements. This work was supported by the Ministry of Sience (project MD ), Russian Foundation tor Basic Reseach (projects , , _mol_a, _mol_a) [1] Levin, V.V.; Zemtsov, A.A.; Struchkova, M. I.; Dilman, A.D. rg. Lett. 2013, 15, [2] Kosobokov, M. D.; Levin, V.V.; Zemtsov, A.A.; Struchkova, M. I.; Korlyukov, A. A.; Arkhipov, D. E.; Dilman, A.D. rg. Lett. 2014, 16,

198 P87 THERMAL AD ALUMIUM XIDE IDUCED GAS-PHASE RIG- PEIG TRASFRMATI F GEM-DIFLUR- AD GEM- FLURCHLRCYCLPRPAES WITH FRMATI F 2- FLUR- R 2-CHLRBUTA-1,3-DIEES.V. Volchkov, M.B. Lipkind, M.A. ovikov,.m. efedov.d. Zelinsky Institute of rganic chemistry of Russian Academy of Sciences, Leninsky prospect 47, , Moscow,Russian Federation It was found that gem-fluorochlorocyclopropanes 1a-d are converted into corresponding 2- fluorobuta-1,3-dienes 3а-d under gas-phase pyrolysis in flow tube-reactor at С as result of thermal cyclopropyl-allylic ring opening transformation and dehydrochlorination. Under analogous conditions gem-difluorocyclopropanes 2a-d undergo only thermal fragmentation with elimination of difluorocarbene to give alkenes. R C l R 1 R 2 4 a -d ( % ) A l C flo w F C l R F R R C R 1 flo w C H 3 1 a -d 3 a -d ( % ) R 1 R 2 R = R 1 = H, R 2 = C H 3 (a ); R 1 = R 2 = H, R = C H 3 (b ); R = R 2 = H, R 1 = C H 3 (c ); R = R 1 = H, R 2 = C l (d ); R R 1 R 2 C H 3 + :C F C flo w F F R R 1 R 2 C H 3 2 a -d A l C flo w The character of thermal transformation of 1a-d and 2a-d is changed if the pyrolysis carry out in the presence of Al 2 3. In this case gem-difluorocyclopropanes 2a-d can be converted into 2-fluorobuta- 1,3-dienes 3а-d at С as result Al 2 3 promoted breaking of very strength carbone-fluorine bond that induce cyclopropyl-allylic transformation and dehydrofluorination. The ability of Al 2 3 to activate the breaking С-F-bond cause also the promotion and the alteration of selectivity for ringopening transformation of gem-fluorochlorocyclopropanes 1a-d. In contraste to homogeneous pyrolysis, heterogeneous thermolysis of 1a-d in the presence of Al 2 3 at С gave 2- chlorobuta-1,3-dienes 4а-d. 198

199 P88 A IMPRVEMET F THE CATALYTIC PERFRMACE I THE ASYMMETRIC MICHAEL REACTI F PRIMARY AMIE TAGGED T A -(CARBXYALKYL)IMIDAZLIUM CATI V.G. Lisnyak, A.S. Kucherenko, S.G. Zlotin IC RAS, Laboratory 11, Moscow, Russia A (1S,2S)-1,2-diphenylethane-1,2-diamine derivative modified with an -(4- carboxybutyl)imidazolium cation and PF6 anion has been developed and applied as a recyclable organocatalyst of the asymmetric 1,4-conjugate addition of 4-hydroxy-2H-chromen-2-one to 1- substituted buten-3-ones or cyclohexen-3-one to afford corresponding Michael adducts in high yields (up to 97 %) and enantioselectivities (up to 90 % ee) [1]. The most active (S)-enantiomer of the clinically useful anticoagulant warfarin was prepared in this way. The catalyst exhibited better recyclability than its known analog [2], which does not contain a carboxy group: it could be recycled 5 times in the reaction without a significant decrease in product yield or ee values. Gradual deactivation of the catalyst was caused by leaching during workup rather than by off-cycle reactions between the catalyst and reagents. The work was financially supported by the Russian Foundation of Basic Research (project ). [1] A. S. Kucherenko, V. G. Lisnyak, A.. Chizhov, S. G. Zlotin, Eur. J. rg. Chem., 2014, [2] A. S. Kucherenko, D. E. Siyutkin, A. G. igmatov, A.. Chizhov, S. G. Zlotin, Adv. Synth. Catal. 2012, 354,

200 P89 SYTHESIS AD SPECTRAL FEATURES F VEL PHTCHRMIC DIARYLETHEES F AZLE SERIES A.G. Lvov 1, E.Yu. Bulich 2, A.M. Yanina 2, A.M. Kavun 3, V.Z. Shirinian 1, M.M. Krayushkin D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - D.I. Mendeleev University of Chemical Technology of Russia, Moscow, Russia 3 - Higher Chemical College, D.I. Mendeleev University of Chemical Technology of Russia, Moscow, Russia Diarylethenes with heterocyclic aromatic moieties are widely studied to develop different electronics devices, such as optical memory and molecular switches [1]. To develop new photochromic systems with improved spectral properties we have proposed a new type of the photochromic diarylcycloalkenones of azole series. Various novel photochromic diarylethenes bearing cyclopentenone or cyclohexenone rings as ethene bridge and azole residues (oxazole, imidazole, pyrazole and thiazole derivatives) as aryl moieties have been synthesized. Ketoesters 1 are the key compounds in these syntheses which were prepared from commercially available reagents in two stages. To introduce diverse functional groups in ethene bridge and aryl moieties the various synthetic methods (C-alkylation, azarov, Michael and Knoevenagel reactions) have been used. 1 Br Ar 2 A r 1 A r 2 A lk y la tio n + K n o e v e n a g e l c o n d e n s a tio n 2 A r 1 1 C 2 Et A r H Ar 2 H Ar A r 1 A r 2 K n o e v e n a g e l c o n d e n s a tio n + a z a ro v c y c liz a tio n Ar 1,2,3 = M e Ar M e R Ar 1 P h Ar 2 P h 4 M e P h M e S P h A r 1 A r 2 M ic h a e l a d d itio n + K n o e v e n a g e l c o n d e n s a tio n (o n e -p o t) M e S M e The spectral characteristics of the obtained photochromic compounds as well as some features of their preparation methods will be also discussed. Acknowledgments: This work was financial supported by Russian Foundation for Basic Research (Grant ). References: [1] M. Irie; Chem. Rev. 2000, 100,

201 P90 EW PHTIDUCED REARRAGEMET F DIARYLETHEES A.G. Lvov 1, A.M. Kavun 2, V.Z. Shirinian 1, V.V. Kachala 1, M.M. Krayushkin D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - Higher Chemical College, D.I. Mendeleev University of Chemical Technology of Russia, Moscow, Russia Diarylethenes (stilbenes) are one of the most reactive systems in photochemistry. Their cis/trans isomerization, [2+2] cycloaddition and photocyclization reactions are widely known. Among them, the photocyclization of diarylethenes is a subject of long standing interest. This process proceeds in accordance with the Woodward-Hoffmann rule by conrotatory 6π-electrocyclization mechanism of the cis-form of stilbenes I leading to the formation of the thermodynamically less stable isomer, 4a,4b-dihydrophenanthrene II, which is used in different transformations depending upon the structure nature and on the reaction conditions, including photochromic switching and the synthesis of polyarenes. R 3 R 4 R 3 R 4 R 1 h X R 2 X X R 2 X I II X : C H = C H,,, S h R 1 e w p ro d u c ts In a continuation of our studies on the photochromic properties of diarylethenes we have found a new skeletal rearrangement resulting in the formation of polycyclic aromatic systems [1]. It was found that the photoreaction of 1,2-diarylethenes 1 comprising oxazole and phenyl rings under UV light yields to amido-substituted polyarenes 3 with high efficiency. H M e h (3 6 5 n m ) CHCl M Ar H M e Ar M e H Ar ( % ) The synthetic features and possible mechanism of the new photorearrangement will be discussed. Acknowledgments: This work was financial supported by Russian Foundation for Basic Research (Grant ) References: [1] A. G. Lvov, V. Z. Shirinian, V. V. Kachala, A. M. Kavun, I. V. Zavarzin, M. M. Krayushkin. rg. Lett. 2014, accepted. 201

202 P91 FRIEDEL-CRAFTS ALKYLATI F FURAS WITH BEZYL ALCHLS CATALYZED BY CPPER(II) SALTS A.S. Makarov, M.G. Uchuskin, A.V. Butin Perm State University, Department of Chemistry, Perm, Russia Friedel-Crafts reaction is known to be one of the most powerful tool for introduction of variety of alkyl groups into furan ring, however the use of strong Bronsted acids or hard Lewis acids leads often to partial destruction of furan substrates due to their acidophobic nature. evetheless, utilization of π-activated alcohols under mild catalytic conditions allows for products to be isolated in reasonable yields [1]. Various expensive Lewis acids are usually used for activation of alcohols [2, 3]. Although several benzyl-substituted furans were synthesized by these procedures in moderate to excellent yields, the substrate scope has not been explored adequately. Thus, the development of a general catalytic procedure for alkylation of furans with benzyl alcohols employing inexpensive catalysts remains an important challenge. Recently we reported a copper vitriol-catalyzed domino-reaction of o-aminobenzyl alcohols with different furfurylamines which provides a simple route to 2-acylvinyl-substituted indoles [4]. ur continuing interest in C-C bond forming reactions led us to examine other copper(ii) salts in the alkylation step. We found that some copper(ii) salts might be used as catalysts for the alkylation of furans 2 with substituted benzyl alcohols 1. Resulting benzyl furans 3 were isolated in good to excellent yields under optimized reaction conditions. R 1 R 1 H + R 2 R 2 R 3 C u II R R 1 = H, A lk, A lk, H a l R 2 = A lk, A r R 3 = A lk, A r Herein, we report a novel copper(ii)-catalyzed Friedel-Crafts alkylation protocol allowing for synthesis of a large variety of substituted benzylfurans. We thank Russian Foundation for Basic Research (RFBR, grant ) and Ministry of Education and Science of Russian Federation ( /K) for the financial support. 1. M. Bandini, M. Tragni, rg. Biomol. Chem., 2009, 7, p S. Roy, S. Podder, J. Choudhury, J. Chem. Sci.,2008, 120, p M. oji et al., Synthesis, 2008, 23, p Uchuskin M. G., Molodtsova. V., Lysenko S. A., Strel'nikov V.., Trushkov I. V., Butin A. V., Eur. J. rg. Chem., 2014, p

203 P92 CATALYTIC CRSS CYCLMAGESIATI F 1,2-DIEES I THE SYTHESIS F Z,Z-DIEIC ALCHLS AD 5Z,9Z-DIEIC ACIDS V.A. Dyakonov, A.A. Makarov, E.Kh. Makarova, U.M. Dzhemilev Institute of Petrochemistry and Catalysis, Russian Academy of Sciences; Laboratory Catalytic Synthesys; Ufa; Russia Intermolecular cross cyclomagnesiation of terminal aliphatic 1 and oxygenated 1,2-dienes 2 was performed for the first time by means of Grignard reagents and Cp 2 TiCl 2 to give, after acid hydrolysis of the reaction mixture, oxygenated hydrocarbons containing a 1Z,5Z-diene moiety 4 in the molecule in up to 94% yields. The developed reaction formed the basis for elaboration of a new effective method for the synthesis of 5Z,9Z-dienoic acids, in view of the published data concerning a broad range of biological activities of these compounds, including, antimalarial, antimicrobial, antitumor, and antiviral activities. Along with low toxicity of С20-С30 acids, this makes these compounds fairly attractive as a base for development of modern medical drugs. We suggested that the developed approach to the synthesis of oxygenated dienes by means of cross cyclomagnesiation could serve as the basis for a new approach to the synthesis of 5Z,9Z-dienoic acids. Thus according to the scheme we proposed, the first step is Cp 2 TiCl 2 -catalyzed cross cyclomagnesiation of terminal aliphatic allenes 6 with the tetrahydropyran ether of hepta-5,6-dien- 1-ol 5 by EtMgBr under conditions developed above. The subsequent hydrolysis of the reaction mixture results in oxygenated dienes 7. The removal of pyranyl protection and oxidation of the 5Z,9Z-diene alcohols 8 thus formed leads to target 5Z,9Z-dienoic acids 9 in 45-48% yields and 98% stereoselectivity. This work was performed under financial support from the Russian Science Fondation (Grant ) 203

204 P93 CYCLALUMIATI F ALKEES AD ALKYES I THE SYTHESIS F PHSPHLAES AD PHSPHLEES A.L. Makhamatkhanova, V.A. Dyakonov, R.A. Agliullina, U.M. Dzhemilev Institute of Petrochemistry and Catalysis of RAS, Laboratory of catalytic synthesis, Ufa, Russia Aluminacyclopentanes 1 and aluminacyclopentenes 2 generated in situ from the cycloalumination reaction of olefins and acetylenes with Et 3 Al catalyzed by 5 mol % Cp 2 ZrCl 2 (toluene, ~ 20 о С, 12 h) were found to undergo the phenyl dichlorophosphine-mediated exchange reaction between aluminum and phosphorus giving rise to practically important 3-alkyl(phenyl)-substituted 1-phenyl phospholanes 3 and 2,3-dialkyl-substituted 1-phenyl 2-phospholenes 4 in high yields after hydrolysis of the reaction mixture. The resultant phosphanes 3 and 4 corresponding readily form oxides and sulfides on treatment with hydrogen peroxide in chloroform or elemental sulfur. The structure of the synthesized compounds has been established by one- ( 1 H, 13 C, Dept 135) and two-dimensional (HSQC, HMBC и HH CSY) MR techniques. The effect of the reagent ratio, duration and temperature of the reaction on the yield of the desired phosphacarbocycles is discussed. This work was supported financially by the Russian Foundation for Basic Research (Grants , ) and Sh U.M. Dzhemilev, A.G. Ibragimov, A.P. Zolotarev, R.R. Muslukhov, and G.A. Tolstikov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1989, 38, V.A. D yakonov, Dzhemilev Reactions in rganic and rganometallic Synthesis; VA Sci. Publ.: ew-york, 2010, 96 p. 3. U.M. Dzhemilev. Mendeleev Commun., 2008, 18,

205 P94 PIEERIG IIC LIQUID-PRMTED UCLEPHILIC ARMATIC CIE-SUBSTITUTI F HYDRGE.. Makhova, M.A. Epishina, A.S. Kulikov.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Rissia The nucleophilic substitution of hydrogen in electron-deficient arenes (S H ) is a general process of great practical value. 1 ver the past decades several variants of S H processes were opened and investigated in details: the oxidative nucleophilic substitution of hydrogen, the vicarious nucleophilic substitution (VS), the cine- and tele-substitution, the ARRC substitution. The cine-substitution is a process, in the course of which the entering nucleophilic group takes up a position adjacent to that occupied by the leaving group. ne of the cine-substitution example is conversion of substituted nitrobenzenes into benzoic acids under the action of KC excess in aqueous EtH (the von Richter reaction). The carboxylic group always enters in orto-position to leaving nitro group. This transformation occurs by heating of different substituted nitrobenzenes in the presence of the KC excess in refluxing 48% aqueous ethanol during h or in a sealed tube at o C during 1-2 h. Yields of final benzoic acids were as a rule low or the expected benzoic acids were not generated at all. In addition, the reaction is accompanied by a large amount of acidic tar, apparently polymeric by nature. In this work we have found that transformation of electron-deficient arenes (nitrobenzene 1a and 4- Cl- (1b), 4-Br- (1c), 4-F- (1d), 4-I- (1e), and 4-Me- (1f) nitrobenzenes) to corresponding benzoic acids 2a-f under the action of the KC excess in aqueous EtH (von Richter reaction) was promoted by ionic liquids (ILs). ur research team has great expertise and successful experience in the performance of various reactions in Ils. 2 Screening of the conditions for the synthesis of m- chlorobenzoic acid 2b from of 4- chloronitrobenzene 1b shown that the optimum molar ratio ionic liquid [bmim]bf 4 :1b is 1.75:1 or 175 mol% of [bmim]bf 4. All tested cases of the von Richter reaction of nitroarenes 1a-f in the presence of ionic liquids proved successful and produced those results which were not possible in before described conditions. The influence of nature of the substituents in nitrobenzenes on the reaction results was revealed the stronger electron-donating properties of substituents, the slower the reaction. This finding is the first case of the nucleophilic aromatic cine-substitution of hydrogen promoted by ionic liquids. 1. F. Terrier, Modern ucleophilic Aromatic Substitution; Wiley-VCH, Weinheim, 2013, 488 pp Makhova, M. I. Pleshchev, M. A. Epishina, A.S. Kulikov, Synthesis and transformation of nitrogen-containing heterocycles in iionic liquids, Khim Heterocycl, Soedin., 2014 (5), (in Russian). This work was supported by Russian Foundation for basic Research (grant a). 205

206 P95 REACTIS F ADDITI F THIPHEL T PRPARGYL SYSTEMS AD BICHEMICAL ACTIVITY F BTAIED CMPUDS V.M. Farzaliyev, P.Sh. Mammadova, E.R. Babayev, H.Sh. Aliyeva, I.M. Eyvazova A.M.Guliyev Institute of Chemistry of Additives of Azerbaijan ational Academy of Sciences (AAS), Beyuk-Shor Str., Block 2062, AZ1029, Baku, Azerbaijan High reactivity of thiols allows to easily conduct thiylling of multiple carbon-carbon bonds. These reactions are convenient methods of synthesis of the various derivatives possessing practically interesting properties, and also they can be considered as modelling ones for some physiologically important processes occurring in live organisms. The research of reactions of nucleophylic, radical and non-catalytic addition of aromatic tiols to acetylene alcohols with account of structure properties of initial reagents gives an opportunity to establish theoretic bases at purposeful synthesis of practically interesting compounds. We synthesized phenyl thioalkenols at the condition of nucleophylic, radical and non-catalytic addition and carried out comparative analysis of results, obtained for all three types of reactions taking into account structure of initial acetylene alcohols (propargyl, methyl -, dimethyl-, and methylethylethynilcarbinols) and thiophenol. The basic parameters, such as molar rate of initial reagents, duration and temperature for these reactions remained to be unchanged. Isomer content and rate of cis-, trans-conformers were established by H 1 MR-spectra. Identification of α and β- isomers was carried out on resonance signals of =CH 2 - and CH=CHgroups, but rate of cis-, trans-conformers was determined by analysis of results of integration with account of constant of spin-spin interaction. H 1 МR-research of reactionary mixture was carried out till its separation to exclude the influence of isomer processes as far as possible. Part of β- isomer (cis- + trans-) was used as quality measure of influence of factors of initial reagents structure on regioselectivity. Under these conditions the part of cis-, trans-conformers was the measure of influence on stereo specificity. Composition, structure and yield of products of reaction of nucleophylic, radical and non-catalytic addition of thiophenol to propargyl systems are determined by electronic (to a lesser degree) and steric factors of the structure of the reacting compounds, mainly, acetylene ones. The direction of the attack (regiodirectivity) is controlled by space difficulties, formed by both reagents at their direct interaction, but stereoselectivity depends on the steric factors of the structure, mainly, thiol compounds. It has been shown that reaction of non-catalytic addition of arylthiols to propargyl systems is a convenient and technologically accessible method for purposeful synthesis of arylthio - and cyclohexylthioamines with high yields. The reaction proceeds, basically, on nucleophylic mechanism and with partial participation of thiyl radicals. There has been revealed high antimicrobial effectiveness of series of the synthesized sulphides in lubricating oils, fuels and cutting liquids. 206

207 P96 A EXPERIMETAL APPRACH FR THE ESTIMATI F CRYSTAL LATTICE EERGY F C-CRYSTAL A.. Manin, A.P. Voronin, G.L. Perlovich G.A. Krestov Institute of solution chemistry of the Russian academy of scienses, "Physical Chemistry of Drugs" department, Ivanovo, Russia The creation of pharmaceutical co-crystals is an area of expanding growth. These materials offer a possible route for the modification of the physicochemical properties of APIs, such as solubility, physical and mechanical properties, thermodynamic stability etc., without changing the pharmacological activity. The key design tool used to select a suitable compound (a co-crystal former) for a given substance is the concept of supramolecular synthon. [1] Several types of supramolecular synthon are usually realized in two-component crystals and are characterized by intermolecular hydrogen bonds (H-bonds) of different types and strengths. The energy of these interactions was evaluated in a number of papers. [2] A lot less attention has been paid to the quantitative description of the intermolecular interactions of homo- and heterodimers with the neighbor molecules which play an important role in the successful co-crystal phase formation. The cumulative characteristic of the intermolecular (noncovalent) interactions in solids is the sublimation enthalpy ΔH sub. This value extrapolated to 0 K corresponds to the crystal lattice energy, E latt. Despite the active investigation of various physicochemical properties of co-crystals, no papers concerning co-crystal sublimation have been published until now. The aim of our study is to provide an experimental validation of the transpiration method for cocrystal enthalpy of sublimation estimation. The present research work considers the co-crystal of 2- hydroxybenzamide (salicylamide, A) with 4-acetamidobenzoic acid (acetamidobenzoic acid, B). This co-crystal is chosen for the following reasons. (i) The acid amide heterosynthon is a persistent H-bond motif in co-crystal structures. (ii) Salicylamide is an active pharmaceutical ingredient while acetamidobenzoic acid is safe for human consumption. (iii) The thermodynamic functions of sublimation for both components have been obtained by us earlier. A novel 1:1 co-crystal of salicylamide and 4-acetamidobenzoic acid was obtained by DSC screening procedure as well as grinding (both neat and solvent-drop) and solvent evaporation techniques. A complete thermal analysis performed by DSC, TG, and hot stage microscopy revealed that the co-crystal remains stable in its solid form until the melting point at C, where it breaks down into components. To determine the optimal conditions of single crystal growth, a triangle phase diagram for the object system with ethanol was built. An X-ray diffraction experiment with complete solving of the crystal structure was carried out for the co-crystal. For the first time in literature, the sublimation thermodynamics of a multicomponent crystal was studied experimentally by the transpiration method in a quasi-equilibrium mode. A presumable mechanism of the sublimation process was proposed with the heterodimer sublimating and eventually dissipating into separate molecules. 1. Desiraju, G. R. Crystal Engineering: From Molecule to Crystal. J. Am. Chem. Soc. 2013, 135, 27, ; 2. Dunitz, J. D.; Gavezzotti, A. Supramolecular Synthons: Validation and Ranking of Intermolecular Interaction Energies. Cryst. Growth Des. 2012, 12, ; This work was supported by the Russian Scientific Foundation ( ). We thank the Upper Volga Region Centre of Physicochemical Research for technical assistance with DSC and XRPD experiments. 207

208 P97 SELECTIVE C-H ALKEYLATI F ARYL ETHERS AD THIETHERS I MIXTURES A.. Marjanov 1, K.V. Luzyanin 1, V.P. Ananikov Laboratory of Cluster Catalysis, Saint Petersburg State University, Universitetsky pr. 26, Stary Petergof, , Russia 2 - Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky Prospekt 47, Moscow, , Russia Direct C H alkenylation of arenes assisted by the directing group represent one of the most atomeconomic approaches for the preparation of 1,2-disubstituted olefines. 1 5 While the alkenylation of single starting material is a well-established strategy, the selective alkenylation of a sole component in a mixture of substrates, is not known. A B S S Y C 2 Et Y 2-(phenylthio)pyridine 2-(phenylsulfinyl)pyridine S X mixtures of three or four substrates oxidant, catalyst solvent, D X C 2 Et single product 2-phenoxypyridine benzyl(phenyl)sulfane Scheme 1. Substrates used for this study (A) and a selective CH alkenylation of a mixture of substrates with ethyl acrylate (B). In pursuit of our studies, we discovered that careful optimization of reaction conditions for C H alkenylation, e.g. solvent, oxidant, catalyst, reaction temperature and ratio of substrates turns out possible a selective alkenylation of a single component in a mixture of substrates. Indeed, several different mixtures of aromatic ethers and thioethers were studied toward ethyl acrylate as alkenylating source (Scheme 1). For each mixture, only a sole component was a subject of alkenylation while all others remained intact. In the current report, we summarize obtained data regarding C H alkenylation of mixtures of ethers and thioethers making a particular emphasis on improving the selectivity of the process and understanding its driving forces. Acknowledgements: This work has been partially supported by the Saint Petersburg State University (research grant from Laboratory of Cluster Catalysis), and the Russian Fund for Basic Research (grant ). [1] García-Rubia, A.; Fernández-Ibánez, M. A.; Gómez Arrayás, R.; Carretero, J. C. Chem. Eur. J. 2011, 17, [2] Yu, M.; Xie, Y.; Xie, C.; Zhang, Y. rg. Lett. 2012, 14, [3] Zhang, X.-S.; Zhu, Q.-L.; Zhang, Y.-F.; Li, Y.-B.; Shi, Z.-J. Chem. Eur. J. 2013, 19, [4] Shi, B.-F.; Zhang, Y.-H.; Lam, J. K.; Wang, D.-H.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, [5] Liu, B.; Jiang, H.-Z.; Shi, B.-F. J. rg. Chem. 2014, 79,

209 P98 SYTHESIS AD CHARACTERIZATI F DEDRIMERS DERIVED FRM GLYCERL B. Menot, J. Stopinski, S. Bouquillon Institut de Chimie Moleculaire de Reims CRS UMR 7312, Universite de Reims Champagne Ardenne UFR Sciences Exactes et aturelles, BP 1039, Reims Cedex 2 France For several years, the laboratory was interested in the development of dendrimers using various organic biosourced by-products, the valuation of which being a real interest for our region. ne of the first explored strategies was based on the decoration of nitrogen-based dendrimers (commercially available polypropyleneimines (PPIs)) [1] with by-products of glycerin. The toxicity of these decorated nitrogenous-based dendrimers was evaluated [2] and their potential in catalysis or in encapsulation demonstrated [1,3]. The synthetic strategy envisaged now by our team is to apply our decoration strategy to commercially available polyamidoamines (PAMAMs) and to synthesize directly from the glycerin new families of dendrimers. The preparation of these last dendrimers directly from biobased building blocks should improve their biodegradation and decrease their toxicity, what is essential for environmental applications. The objective of this presentation is to present our preliminary results concerning the development of these new glycerodendrimers [4]. [1] S. Balieu, A. El Zein, R. De Soussa, F. Jérôme, A. Tatibouët, S. Gatard, Y. Pouilloux, J. Barrault, P. Rollin, S. Bouquillon, Adv. Synth. Catal. 2010, 352, [2] S. Balieu, C. Cadiou, A. Martinez, J.-M. uzillard, J.-B. udart, F.-X. Maquart, F. Chuburu, S. Bouquillon, J. Biomed. Mater. Res. Part A 2013,101A (3), [3] K. Fhayli, S. Gatard, A. Mohamadou, L. Dupont, S. Bouquillon, Inorg. Chem. Comm. 2013, 27, 101. [4] B. Menot, J. Stopinski, A. Martinez, S. Bouquillon, publication in preparation. 209

210 P99 PALLADIUM-CATALYZED HIGHLY REGISELECTIVE PHSPHATI F MES-USUBSTITUTED PRPHYRIS VIA C(sp 2 )-H FUCTIALIZATI E.A. Mikhalitsyna, E.S. Podyacheva, I.P. Beletskaya MSU Faculty of Chemistry, Moscow, Russia Synthesis of new artificially modified porphyrins has received much attention as a very attractive and promising goal for catalysis, medicine, light-absorbing materials mimicking the antenna complexes of photosynthetic system, photovoltaics etc. 1 In our work we are focused on the development and optimization of high regioselective C-H phosphonation of porphyrins and their metal complexes in meso-position via oxidative Pd(II)-catalyzed dehydrogenative cross-coupling (CDC). Surprisingly, to the best of our knowledge, there are very few catalytic examples regarding the C(sp 2 ) P bond formation through direct phosphonation of the C H bond with phosphite ester including a limited class of compounds with acid C-H bond such as coumarins, azoles, terminal alkynes and α amino ketones. 2-5 We herein report the first example of the catalytically oxidative phosphonation of meso-unsubstituted porphyrins, which has attracted great attention for excellent atom economy and an enviromentally friendly approach in opposite to classical tremendous multistep synthesis. 6 To study the influence of structural factors on the reactivity of porphyrin substrates the target series of meso- tris-, di- and mono-mesityl substituted porphyrins and their i(ii) and Zn(II) metal complexes were synthesized by condensation of corresponding dipyrrylmethanes with mesitylaldehyde in the presence of an acid catalysts and oxidant. 7 Pd(II)-catalyzed C-H posphonation of i(ii) 5-mesitylporphyrin (ipmes) was successfully carried out with 40 mol% Pd(Ac) 2 as catalyst, 1.2 eq. of 4,4 -bipyridine as ligand, 6 eq. of K 2 S 2 8 as oxidant and excess of diethyl phosphite in refluxed dioxane under air atmosphere during 24 hours (Fig. 1). Target monophosphotated product were obtained and separated by column chromatography in good 80% yield along with 14% of bis-phosphonated product. The same conditions were used for phosphorylation of bis-5,10-dimesityl and tris-5,10,15-trimesitylporphyrins to prepare in 42% and 29% mono- and diphosphonated porphyrins correspondingly. Fig. 1. Pd-catalyzed C-H phosphonation of 5-mesitylporphyrin 1. J. Mack, Z. Shen,. Kobayashi. In Handbook of Porphyrin Science; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; World Scientific Publishing: Singapore, 2012; Vol. 23, pp X. Mi, M. Huang, J. Zhang, Ch. Wang and Y. Wu, rganic Letters, 2013, 15, pp Ch. Hou, Yu. Ren, R. Lang, X. Hu, Ch. Xia and F. Li, Chem. Commun., 2012, 48, pp Y. Gao, G. Wang, L. Chen, P. Xu, Y. Zhao, Y. Zhou and L.-B. Han, J. Am. Chem. Soc., 2009, 131, B. Yang, T.-T. Yang, X.-A. Li, J.-J. Wang and S.-D. Yang, rg. Lett., 2013, 15, 19, Yu. Y. Enakieva, A. G. Bessmertnykh, Yu. G. Gorbunova, Ch. Stern, Y. Rousselin, A. Y. Tsivadze and R. Guilard, rganic Letters, 2009, 17, pp Ch. Brückner, J. J. Posakony, C. K. Johnson, R. W. Boyle, B. R. James and D. Dolphin, J. Porphyrins Phthalocyanines, 1998, 2, pp

211 P100 SYTHESIS AD REACTIVITY F 7-AMI-4-X-3-R-8-R -6H- PYRAZL[5,1-C][1,2,4]TRIAZIES L.M. Mironovich, D.V. Shcherbinin, A.Y. Podolnikova Southwest State University, Basic Chemistry and Chemical Technology, Kursk, Russia Reactivity of the 1,2,4-triazine derivatives containing pyrazole ring in the structure is now intensively studied. 7-Amino-4-oxo-3-R-8-R -6H-pyrazolo[5,1-c][1,2,4]triazines (2,3) has been synthesised by refluxing compound (1) with malononitrile and ethyl cyanoacetate in the medium pyridine [1]. Boiling of compound (2) with KH in the alcoholic medium has led to hydrolysis with isolation of compound (4), it was treated with HCl and received pyrazolo[5,1-c][1,2,4]triazine-8-carboxylic acid (5). Decarboxylation at high temperatures leads to isolation of compound (6). Pyrazolo[5,1- c][1,2,4]triazine-8-carbohydrazide (7) obtained by boiling compound (2) with 2 H 4 in the alcoholic medium. Refluxing of compound (3) in the alkaline medium has led to carbamide (8). Boiling of compound (8) with formic acid has led to pyrimido[4,5 :3,4]pyrazolo[5,1- c][1,2,4]triazines (10). The structure of compound (10) was determined by X-ray crystallography. For fant of reflux P 2 S 5 in pyridine with compound (10) leads to 4,11-dithioxo-3-R-6H,10Hpyrimido[4,5 :3,4]pyrazolo[5,1-c][1,2,4]triazine (11) and 11-oxo-4-thioxo-3-R-6H,10Hpyrimido[4,5 :3,4]pyrazolo[5,1-c][1,2,4]triazine (12). -(3-tert-butyl-4,8-dithioxopyrazolo[5,1- c][1,2,4]triazin-7-yl)аmid metadithiophosphorous acid (9) (348 [M + ]), was received from the responding compounds (3). The structures of the synthesized compounds are confirmed with spectral methods (IR, H 1 -MR-, mass spectra) and elemental analysis data. Compounds show weak antimicrobial activity. [1] Mironovich, L.M. and Kostina, M.V. // Russian Journal of rganic Chemistry, 2011, vol. 47, 12, P

212 P101 HYBRID MATERIALS BASED CPPER AD PALLADIUM CMPLEXES F (1,10-PHEATHRLYL)PHSPHATES FR CATALYSIS A.Yu. Mitrofanov 1, A.G. Bessmertnykh-Lemeune 2, R. Guilard 2,.S. Goulioukina 1, I.P. Beletskaya A.. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, 31-4 Leninskiy p., Moscow, , Russia 2 - Institut de Chimie Moleculaire de Universite de Bourgogne (ICMUB), UMR CRS 6302, 9 avenue A. Savary, 21078, Dijon Cedex, France Considerable attention has been attached recently to the immobilization of transition metal complexes onto solid supports to prepare advanced catalytic systems [1]. Using this approach, it is expected to increase catalyst stability and allow for catalyst recycling and product separation. rganophosphonates are of interest for this field due to their simple synthesis and high reactivity towards various metal salts and alkoxides. In fact, different ligands can be easily decorated by the phosphonate group for immobilization onto thermally and mechanically stable metal oxide matrices. Herein we describe the results of our studies on the functionalization of titania by copper(i) and palladium(ii) complexes with (1,10-phenanthrolyl)phosphonates (Pphen) recently described by us (Figure) [2]. Figure. Copper(I) and palladium(ii) complexes with Pphen. The covalent grafting of the complexes was performed according to two routes. The first one, socalled one-pot synthesis, involves a co-condensation step between a complex with an inorganic precursor (titanium isopropoxide) according to the sol-gel technique. In the second one, so-called post-functionalization, а chemical surface modification of a preformed mesoporous titanium(iv) dioxide (S BET = 650 m 2 /g) through chemical bonds between the hydroxyl groups covering the pore surface and complexes is used. The structural and textural properties of these hybrid materials will be presented and explained based on a solution behavior of the studied complexes. High catalytic activity of newly synthesized hybrid materials in the palladium-free Sonogashira reaction, the copper-catalyzed boration of alkynes and Suzuki reaction are reported and examples of catalyst recycling are given. Acknowledgements: This work was carried out in the frame of French-Russian Laboratory LAMREM of CRS and RAS and supported by Russian Foundation for Basic Research (grant # ). [1] Suib, S. L. ew and Future Developments in Catalysis, Elsevier: Amsterdam, [2] (a) Mitrofanov, A. Yu., Bessmertnykh-Lemeune, A., Stern, C., Guilard, R., Gulyukina,. S., Beletskaya, I. P. Synthesis, 2012, 44, (b) Mitrofanov, A. Yu., Manowong, M., Rousselin Y., Brandes S., Guilard, R., Bessmertnykh-Lemeune, A., Chen, P., Kadish, K. M., Goulioukina,., Beletskaya, I. Eur J. Inorg. Chem., 2014, DI: /ejic

213 P102 SYTHESES, STABILITIES AD REACTIVITIES F ALKYYL(ARYL)IDIUM SALTS W.J. Moran University of Huddersfield, Department of Chemistry, Huddersfield, UK Iodonium salts are increasingly popular reagents in organic synthesis because of the range of useful reactivities that they exhibit. 1 The most investigated iodonium salts are the diaryliodonium salts, which can, in principal, donate either of their aryl groups in reactions with nucleophiles (Scheme 1). 2 In contrast, alkynyl(aryl)- and alkenyl(aryl)iodonium salts only donate the alkyne or alkenyl groups respectively. This means that the aryl iodide group is, essentially, a spectator group in these two types of iodonium salts. However, the effect of changing this spectator group on the reactivity of these salts has not been studied. 3 Scheme 1. General reactivities of iodonium salts with nucleophiles highlighting the spectator role of the aryl iodide in alkenyl- and alkynyl(aryl)iodonium salts ur study on the preparation of a range of alkynyl(aryl)iodonium salts directly from terminal alkynes and aryl iodides and the stabilities and reactivities of these salts will be discussed. 4 Surprisingly, we found a marked increase in the stability and reactivity of iodonium salts derived from 2-iodoanisole (Scheme 2). I will also present our results on generating alkynyl(aryl)iodonium salts from alkynylsilanes and reacting them directly resulting in yield augmentations of up to 50% compared to the iodobenzene parent. Scheme 2 Direct syntheses of alkynyl(aryl)iodonium salts and the effect of the aryl iodide substituents on stabilities and reaction yields 1. For reviews of iodonium salts in organic synthesis, see: a) M. S. Yusubov, A. V. Maskaev, V. V. Zhdankin, Arkivoc, 2011, i, 370; b) E. A. Merritt, B. lofsson, Angew. Chem., Int. Ed., 2009, 48, 9052; c) T. kuyama, Acc. Chem. Res., 2002, 35, M. Fujita, E. Mishima, T. kuyama, J. Phys. rg. Chem., 2007, 20, Selected examples of reactions with alkynyl(phenyl)iodonium salts: a) B. L. Williamson, P. J. Stang, A. M. Arif, J. Am. Chem. Soc., 1993, 115, 2590; b) B. L. Williamson, R. R. Tywinski, P. J. Stang, J. Am. Chem. Soc., 1994, 116, 93; c) M. chiai, K. Miyamoto, T. Suefuji, S. Sakamoto, K. Yamaguchi, M. Shiro, Angew. Chem. Int. Ed., 2003, 42, 2191; examples of reactions with alkenyl(phenyl)iodonium salts: d) M. G. Suero, E. D. Bayle, B. S. L. Collins, M. J. Gaunt, J. Am. Chem. Soc., 2013, 135, 5332; e) T. kuyama, M. Fujita, Acc. Chem. Res., 2005, 38, D. J. Hamnett, W. J. Moran manuscript submitted for publication. 213

214 P103 MATHEMATICAL MDELIG F DYAMICS F PHTCHEMICAL REACTIS AT THE QUATUM AD THE CLASSICAL DESCRIPTI F THE RADIATI FIELD V.A. Morozov,.D. Chuvylkin, E.A. Smolenskii. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, Moscow, Russia Are examples of differences between the results of using two methods of mathematical modeling of dynamics of populations of the states of the molecule in photochemical reactions. The first method is based on the solutions of the Schrodinger equation for the probability amplitudes of the population of states of the molecule and the radiation field is described by quantum theory. When using a three-level model of the molecule, these solutions are obtained analytically. The second method is based on numerical solutions of the equations for the density matrix elements of the molecule interacting with the classically described irradiation and phenomenological decay of excited states of molecules. The differences formalisms used methods and an underlying conceptions of the physical sense of the light transformation by molecules in photochemical reactions are discussed. 214

215 P104 SYTHESIS F SPIRCYCLPRPYL MALYL PERXIDE FRM CYCLPRPYL MALIC ESTER.M. Mulina, V.A. Vill, A.. Terentiev.D. Zelinsky Institute of rganic Chemistry of Russian Academy of Sciences, Laboratory for Studies of Homolytic Reactions, Moscow, Russia Cyclic diacyl peroxides were in use in oxidation reactions in the s [1]. At the present time, great attention is attracted to these compounds [2]. An unique property of such spirocyclic diacylperoxides as malonyl and phtaloyl ones is their capability to oxidate unsaturated compounds without any catalysts alternatively to their linear analogues, for example commercially available benzoylperoxide and succinylperoxide, and widespread peroxy cycles: ozonides and tetraoxanes. Among malonyl peroxides a spirocyclopropyl malonyl peroxide is the activest and the most frequently used oxidant. It has the lowest molecular weight among familiar malonyl peroxides [2a], and this fact makes the oxidation process more atom-efficient. The main procedure of synthesis of spirocyclopropyl malonyl peroxide 2 is the reaction of spirocyclopropyl malonic acid with % hydrogen peroxide [3] or hygrogen peroxide and urea hydrogen peroxide [2a] in the presence of methanesulfonic acid (Scheme 1). In the present work we succeeded in synthesis of peroxide 2 in the reaction between spirocyclopropyl malonic peroxide 1, which can be easily synthesised by alkylation of diethyl malonic ester with 1,2-dichlorethane in high yields %, and hygrogen peroxide and urea hydrogen peroxide in the presence of methanesulfonic acid. This method makes the synthesis of spirocyclopropyl malonyl peroxide 2 dramatically easier, because it excludes come chemical and procedural steps. 1. (a) W. Adam, J. W. Diehl., J. Chem. Soc., Chem. Commun., 1972, 13, (b) C. L. Perrin, T. Arrhenius, J. Am. Chem. Soc., 1978, 100, (a) J. C. Griffith, K. M. Jones, S. Picon, M. J. Rawling, B. M. Kariuki, M. Campbell,. C.. Tomkinson, J. Am. Chem. Soc., 2010, 132, (b) M. Schwarz,. Reiser. Angew. Chem. Int. Ed., 2011, 50, (c) C. Yuan, A. Axelrod, M. Varela, L. Danysh, D. Siegel, Tetrahedron Lett., 2011, 52, (a) W. Adam, R. Rucktäschel, J. Am. Chem. Soc., 1971, 93, (b) M. J. Darmon, G. B. Schuster, J. rg. Chem., 1982, 47,

216 P105 HYPTHETICAL REACTI MECHAISM F H 2 -ASSISTED -C 6 H 14 - DEX VER Ag/Al 2 3 CATALYSTS A.I. Mytareva,.A. Sadokhina, G.. Baeva, A.Yu. Stakheev.D. Zelinsky Institute of rganic Chemistry, Moscow, Russia Since Satokawa et al. [1] discovered that the low temperature activity of Ag/Al 2 3 in HC-SCR of x can be boosted by addition of small amounts of H 2, the nature of hydrogen effect has been studied intensely. However the mechanism of H 2 -assisted HC-SCR of x is still debated and several solutions have been proposed. ne of the possible pathways involves H 2 -promoted formation of 3 surface species, followed by their transformation to reactive 2 species, which further react with activated HCs. In the present study in order to evaluate possible contribution of this pathway into overall H 2 -assisted HC-SCR over Ag/Al 2 3, we compared the rate of H 2 -assisted C 6 H 14 Dex in steady-state and the rate of 3 surf. reduction by C 6 H 14 in the presence and the absence of H 2. It was repeatedly shown by FTIR and TPD that addition of H 2 into reaction mixture results in the intensive formation of 3 surf., located on Ag species and Al 2 3 surface. This process is very fast and leads to the complete removal of x from the reaction mixture until saturation of the catalyst surface is attained. Surface reaction of 3 surf. species with the feed containing 1000 ppm C 6 H 14 revealed their inertness with respect to HC reductant. n the other hand surface reaction with or H 2 leads to 3 surf. 2 surf. transformation as evidenced by intensive 2 evolution, and in situ XPS data. It should be noted that was found to be more effective in 3 surf. 2 surf. transformation, as compared to H 2, particularly at the reaction temperature below ~ 180 C. Transformation of 3 surf. into 2 surf. greatly enhances reactivity of surface -containing species, and 2 surf. species are rapidly reduced into 2 in the course of the surface reaction with 300 ppm C 6 H ppm H 2. It was found that the rate of 3 surf. reduction by hydrocarbons in the presence of H 2 is identical to the rate of H 2 -HC-SCR of x in steady state. This observation suggests significant contribution of 3 surf. reduction in the rate of the overall HC-SCR mechanism at C. These results appear to be in a good agreement with the literature data on the transient measurements of H 2 -assisted Dex over Ag/Al 2 3 [2-3]. References: [1] S. Satokawa// Chem. Lett., 2000, 29, 294 [2] J.P. Breen, R. Burch and C.J. Hill// Catal. Today, 2009, 145, 34 [3] S. Chansai, R. Burch, Ch. Hardacre, J. Breen and F.J. Meunier// J. Catal., 2010, 276,

217 P106 DEPEDECE F THE SPECIFIC ACTIVITY THE PLATIUM PARTICLE SIZE I THE DEEP XIDATI F C 1 - C 6 RMAL ALKAES A.M. Batkin 1, A.Yu. Stakheev 1, I.E. Beck 2,.S. Teleguina 1, G.. Bragina 1, V.I. Zaikovsky 2, Yu.V. Larichev 2, V.I. Bukhtiyarov D. Zelinsky Institute of rganic Chemistry, Moscow, Russia 2 - Boreskov Institute of Catalysis SB RAS, ovosibirsk, Russia The deep oxidation of volatile organic compounds (VCs) over supported catalysts based on noble metals (Pt, Pd) is among the main exhaust gas aftertreatment technology for mobile machinery and stationary applications. ne of the most important factors influencing the efficiency of noble metal catalyst is the size of metal particles. High Pt dispersion improves utilization of noble metal since increases the fraction of atoms accessible for a reaction. n the other hand, very small metal particles may be ineffective in the reactions requiring multi-atomic surface active sites (structuresensitive reactions). The influence of the metal particle size on the total and specific catalytic activity (SCA, or atomic activity) in deep oxidation was extensively studied. A comparison between experimental data obtained by independent authors allowed us to suppose that the structural sensitivity of deep oxidation and the size effect of the platinum particles on the specific catalytic activity can also be dependent on the structure (first of all, on the size) of the hydrocarbon molecule. In this study we compared the effect of Pt particle size on the activity in catalytic combustion of normal alkanes with different hydrocarbon chain length (C 1 C 6 ) over a series of 0.8% Pt/Al 2 3 with different average Pt particle sizes ranging from 1 to 12 nm. It was established that the range in which specific catalytic activity changes depends substantially on the carbon chain length of the n-alkane. In the oxidation of CH 4 or С 2 H 6, atomic activity increases approximately 2 3 times as the Pt particle size changes from 1 to 11 nm. In propane oxidation, SCA increases approximately by a factor of 5 6, whereas in the oxidation of n-c 4 H 10 and n-c 6 H 14, the specific activity increases 20 and 25 times, respectively. Thus, the structural sensitivity of the deep oxidation of n-alkanes increases with an increase in the size of the hydrocarbon molecule being oxidized. It was found that the catalysts with the maximum degree of dispersion of platinum (d Pt = 1 2 nm) exhibit the highest total activity in the oxidation of small molecules. The catalysts consisting of larger Pt particles (3 6 nm) are most active in the oxidation of longer n-butane and n-hexane molecules, whereas the activity of the finer catalysts is substantially lower. Acknowledgement: Financial support by RFBR grant # a is gratefully acknowledged 217

218 P107 CMPSITE CATALYSTS [Fe-BETA + REDX] FR CMBIIG CATALYTIC PRCESSES: 1) H 3 -SCR AD H 3 -SLIP REMVAL, 2) T 2 XIDATI AD FAST SCR A.I. Mytareva 1, G.. Baeva 1, D.A. Bokarev 1, A.Yu. Stakheev 1, P. Selvam D. Zelinsky Institute of rganic Chemistry, Moscow, Russia 2 - Indian Institute of Technology-Madras, ational Centre for Catalysis Research and Department of Chemistry, Chennai, India Combining several catalytic processes over single catalyst is the general trend in modern heterogeneous catalysis. We explored this approach to develop catalytic systems for environmental protection selective catalytic reduction of x by ammonia (H 3 -SCR). H 3 -SCR is of theoretical and practical interest for abatement x emission from automotive (diesel engines) and stationary (power plants) sources. Recently, H 3 -SCR can be achieved by using catalytic systems based on Fe-Beta or Cu-Beta. However, these catalysts have two main drawbacks: 1) insufficient x conversion at cold-start condition ( ºC), and 2) H 3 -slip problem due to incomplete conversion or exhaust temperature upswings. We attempted to solve these problems by using composite catalysts [Fe-Beta + Redx] comprising H 3 -SCR and Redx functions. 1. Combining H 3 -SCR and H 3 -slip removal According to our recent results Fe(Mn)MCM-48 can be used as Redx components due to high activity in H 3 oxidation process. Therefore composite catalyst was prepared by mechanical mixing of Fe-Beta and Fe(Mn)MCM-48 components. It was shown that mechanical mixing of Fe-Beta with Fe(Mn)MCM-48 allowed us to combine favorable H 3 -SCR performance of Fe-Beta (1) and activity of Fe(Mn)MCM-48 in H 3 oxidation (2) in one catalytic brick H 3 + ½ 2 3 H over Fe-Beta (1) 4 H H 2 over Fe(Mn)MCM-4 (2) Varying the ratio of the components, optimum SCR and H 3 -slip removal performance of composite catalyst can be achieved. Moreover [Fe-Beta + Fe(Mn)MCM-48] demonstrates low 2 emission. 2. Combining oxidation and H 3 -SCR Ce 2 -Zr 2 demonstrates high activity in oxidation to 2. Furthermore, it was found, that the activity can be further boosted, viz. modification by manganese. In this study Mn/Ce 2 -Zr 2 was mixed with Fe-Beta for enhancing low-temperature H 3 -SCR activity of zeolite component. It was found that mixing of zeolite and Redx component leads to a significant increase in x conversion at ºC. This synergistic effect can be attributed to combination of two processes: oxidation over Mn/Ce 2 -Zr 2 (3) followed by the Fast SCR (4) on Fe-Beta over Mn/Ce 2 -Zr 2 (3) H 3 3 H over Fe-Beta (4) Acknowledgments This work was supported by the Russian Foundation for Basic Research (Grant: /ID_a) and Department of Science and Technology, ew Delhi (Grant: IT/RUS/RFBR/P- 152). A. Mytareva is grateful to Haldor Topsøe A/S for financial support in the framework of Ph.D. student support programme. 218

219 P108 CATALYTIC EFFICIET APPRACH T SUBSTITUTED 2,3,4,9- TETRAHYDR-1H-XATHE-1-ES - A GRUP F RALLY ACTIVE EURPEPTIDE Y Y5 RECEPTR ATAGISTS FRM SALICYLALDEHYDES AD DIMEDE R.F. asybullin,.. Sokolova, M.. Elinson.D. Zelinsky Institute of rganic Chemistry, Moscow, Russia Functionally substituted tetrahydro-1h-xanthen-1-ones have received considerable attention in the field of medicinal chemistry due to their useful biological properties and applications [1]. Recently it has been found that tetrahydro-1h-xanthen-1-ones are orally active and selective Y5 antagonists [2]. Known methods for the synthesis of tetrahydro-1h-xanthen-1-ones have its merits and suffer from disadvantages such as long reaction times, moderate yields or complicated work-up procedures. Thus, the development of an efficient and facile method for the synthesis of tetrahydro- 1H-xanthen-1-ones is in high demand. In the present study we report our results on thermally induced non catalytic transformation of salicylaldehydes and dimedone into substituted tetrahydro-1h-xanthen-1-ones (Scheme 1). The reaction is performed in ethanol under 3 min reflux. Corresponding 9-(2-hydroxy-4,4-dimethyl-6- oxo-1-cyclohexen-1-yl)-3,3-dimethyl-2,3,4,9-tetrahydro-1h-xanthen-1-ones were formed in excellent 85-95% yields. Scheme 1 In conclusion, simple non catalytic system can produce, under neutral conditions, a very fast (3 min) and selective transformation of salicylaldehydes and dimedone into tetrahydro-1h-xanthen- 1-ones the orally active and selective Y5 antagonists and the promising heterocyclic compounds for different biomedical applications. The procedure utilizes simple equipment; it is easily carried out and is valuable from the viewpoint of environmentally benign diversity-oriented large-scale processes. Acknowledgements The authors gratefully acknowledge the financial support of the Russian Foundation for Basic Research (Project o ). References 1. H. K.Wang, S. L. Morris-atschke, K. H. Lee, Med. Res. Rev., 1997, 17, S. Mashiko, A. Ishihara, H. Iwaasa, H. Sano, Z. da, J. Ito, M. Yumoto, M. kawa, J Suzuki, T. Fukuroda, M. Jitsuoka,. R. Morin, D. J. Maceil, L. H. T. Van der Ploeg, M. Ihara, T. Fukami, A. Kanatani, Endocrinology, 2003, 144,

220 P109 SLUBILITY AD STRUCTURE F CHITSA I AQUEUS MEDIA F VARIUS ACIDITY. MLECULAR DYAMIC STUDY V.S. aumov, S.K. Ignatov, A.G. Razuvaev, A.E. Mochalova, I.A. Glazova, L.A. Smirnova.I. Lobachevsky State University of izhny ovgorod, Russia Polyaminoglucanes, particularly, chitosan (poly-1,4-(-acetyl)-β-d-2-glucopyranoseamine) are considered today as promising means for encapsulating the protein-contaning drugs ensuring their transport inside an organism. This task is, however, complicated by the lack of information about the structure of the chitosan complexes in aqueous solutions, their thermodynamic properties and kinetics of complexation. In particular, the structure of chitosan chains in the aqueous solution based on the data of electron microscopy was a subject of discussion [1]. Data on the complexation constants with various protein agents are virtually absent, and the details of dissolution kinetics are mostly studied on the basis of formal kinetic approach or without adrressing to the protonation effects [2,3]. In the present study, we use the molecular dynamics (MD) simulations in order to elucidate the details of nanocrystalline chitosan dissolution, the influence of amino group protonation, and kinetics of its dissolution at various acidity of aqueous media. The model system was a chitosan nanocrystal surrounded by the water molecules (SPC water model) and counterions (Cl - ) compensating the protonated amino group charges. The simulation box size was 12.4 x 11.7 x 20.8 nm (~ atoms in total, ~ water molecules). The nanocrystal was consisted of 8 chains of 20 monomeric units (3.2 kda per chain). The initial crystal structure was constructed on the basis of XRD data [4]. Some of amino groups were protonated in the crystal with the protonation degree (PD) corresponded to the ph values from 5.3 to ~7.2. Calculations were performed with GRMACS using the force field GRMS 53A6Carbo [5], specially improved for better polyaminoglycane unit description. Force field modification was perfromed on the basis of quantum chemical calculations (HF/ST-3G//B3PW91/6-31++G(d,p)). Simulation period was up to 10 ns with integration step of 1 fs in the VT-ensemble at 300K, controlled by the Berendsen thermostat. It was found that, at the beginning of dissolution process, the nanocrystal undergoes the remarkable twist-like deformation resulting to the compact bunches of chitosan chains. Then, at PD>0.3, the bunches undergo slow dissociation which rate is determined by the quantity of protonated amino groups. The time-dependency of dissolution degree (measured as an average distance between chains) is almost linear during 10 ns of simulations. The dissolution rate estimated as the time derivative of average distance between chains is also linearly dependent on PD, with threshold of dissolution about PD=0.3 (ph~6.8) which agrees well with available experimental data. The final structures of chitosan after 10 ns of dissolution in aqeous media of various acidity are shown in Figure. [1] Pedroni V.I., Schulz P.C., Gschaider M.E., Andreucetti. Colloid Polym Sci, 2003, 282, 100. [2] Franca E.F., Lins R.D., Freitas L.C.G., Straatsma T.P. J. Chem. Theory Comput, 2008, 4, [3] Franca E.F., Freitas L.C.G., Lins R.D. Biopolymers, 2011, 95, 448. [4] Yui T., Imada K., kuyama K.,bata Y.,Suzuki K.,gawa K. Macromolecules, , [5] Hansen H.S., Hünenberger P.H. J Comput Chem, 2011, 32, 998. This work was supported by the RFBR (Project o , ) 220

221 P110 THE STEAM SMTIC EGIE WITH THE ICREASED EFF T 50% P.A. azarov Russian Chemical Technology University named after D.I. Mendeleev,Chair of Processes and devices of chemical technology position,moscow.russia The evolution of heat osmotic engine [2] on the prototype[1] is to increase the temperature (T 1 =380С) of the left part of the circuit(fig.1) the engine in changing the phase state of the water from liquid to gas, but also adding a second stage of desalination by electrodialysis. Due to the process "steam" or osmosis process of rapid diffusion of water vapor molecules through the membrane into the liquid solution inside the reactor 3(fig.1) osmosis increases the specific power of the engine(w/kg engine ), as well as its efficiency. Steam osmotic engine[2] repeats energy cycle thermal power plant, but through a process of "steam" osmosis and because of the lack of vapor condensation (in the cooler) its efficiency is much higher. Ideal efficiency manual 2-nd Carnot's theorem is(fig.1): EFF= [(T 1 T 2 )/T 1 ]х100% = [(380С 20С)/380С]х100%=[( )/653]х100%=55% (1) Given the mechanical losses in the pump Pump1, 2; formula for calculating the efficiency takes the form. EFF мах ={( W pumps )/ Q}= [(T 1 T 2 )/T 1 ] W pumps = [(P 1osmosis P 2reverse osmosis )/P 1osmosis ] W pumps (2) Where [W] - output power of osmotic (hydraulic) flow P turbines =224,1at; ΔQ [W] - The amount of heat in heat generators 1,2 to keep the system in a given thermal regime (the left side of the technological scheme T 1 =380C=653k, right side T 2 =20C=293k); W pumps [W] - power pumps1,2. Steady state operation of the scheme of steam osmotic engine T 1 = C, T 2 =20-40C. fig.1 References 1. Patent of USA on , Metod and apparatus for generating power utilizing pressure-retarted osmosis. Inventor Sydney Loeb, the Bulletin, , The application for the patent of the Russian Federation from , «Method of reception of mechanical energy and the steam osmotic engine for its realisation» / the applicant and the legal owner azarov P. A. 221

222 P111 THE USATURATED CARB-CARB BD HYDRGEATI I PRESECE F APARTICLES F THE Fe-i GRUP D.. ebykov, V.M. Mokhov, Yu.V. Popov Volgograd State Technical University, Chemical Technology Faculty, Volgograd, Russia The hydrogenation of unsaturated substances and arenes is a widely used industrial process, but it proceeds in harsh conditions or requires using of expensive catalysts. We discovered some methods, giving an ability to carry out the reduction of different substituted alkenes and arenes without using of high temperatures and pressures or expensive materials by means of using ferrous, cobalt or nickel nanoparticles as catalysts. The advantage of methods is in combination of metal nanoparticles synthesis and organic substance hydrogenation. The nano-catalyst is formed from inexpensive metal salts by their reduction with complex borohydrides or alumohydrides or by hydrazine hydrate in solutions, in some cases proceeds in situ hydrogenation of unsaturated bonds. The essential interest deserves a method of liquid phase alkenes hydrogenation with gaseous hydrogen at atmospheric pressure, which is a widely used and inexpensive industrial reagent. Using of simply obtained from accessible and inexpensive substances metal nanoparticles is able to decrease the cost and energy losses comparing to traditional hydrogenation methods. The investigations showed an ability of the carbon-carbon unsaturated bond hydrogenation at very smooth conditions - atmospheric pressure and near room temperatures. Also was found that change of hydrogenating agent, catalyst and it's preparing conditions makes possible to direct the process selectivity and also to reduce some functional groups. As starting materials for hydrogenation were used different derivatives of norbornene, styrene, linear and cyclic alkenes, heterocyclic compounds. References 1. Colloid and nanodimensional catalysts in organic synthesis: I. Investigation of hydrogenation selectivity of unsaturated compounds with hydrazine hydrate and aluminum hydride / Popov Yu.V., Mokhov V.M., ebykov D.. // Russian Journal of General Chemistry Vol. 84, o C Colloid and nanodimensional catalysts in organic synthesis: II. The hydrogenation of alkenes with hydrogen at atmospheric pressure / Popov Yu.V., Mokhov V.M., ebykov D.. // Russian Journal of General Chemistry Vol. 84, o C Hydrogenation of unsaturated carboxylic acids/ Mohov V.., Popov Y.V., ebykov D..// Izvestiya VolGTU, Series Chemsitry and technology of organoelemnt monomers and polymeric materials Iss 12. Mezhvus.sb.nauch.st./VolGTU. Volgograd, 2014, 7 (134) C

223 P112 SYTHESIS AD IVESTIGATI F FUGICIDAL ACTIVITY F 6- BRM-4-HYDRXY-2-PHEILIDLE.D. everova, M.D. Dutov, S.A. Shevelev, G.V. Bastrakova,.V. Serushkina, K.E. Aisina, S.V. Popkov. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, Moscow, Russia Recently, we showed high fungicidal activity of the 2-aryl-4-hydroxy-6-nitroindoles [1]. The presence of the nitro group in these compounds, of course, reduces their value as fungicides, as in the case of use as agricultural agents, and in the case of drugs. Therefore it is very important task to replace the nitro group to an appropriate electronegative substituent, as which, by analogy with Arbidol, we have chosen a bromine atom. Synthesis of the title compound (1) was carried out as follows: It is shown that 6-bromo-4-hydroxy-2-phenylindole outperforms standard triadimefon by fungitoxicity with respect to all the examined fitopatagence not inferior nitro analog. Compound Mycelium growth inhibition, % (С = 30 μg ml -1 ) V.i.* R.s. F.o. F.m. B.s. S.s Triadimefon The authors thank the Russian Foundation for Basic Research (Grant o ) for financial support [1] G. V. Kokurkina, M. D. Dutov, S. A. Shevelev, S. V. Popkov, A. V. Zakharov and V. V. Poroikov, European Journal of Medicinal Chemistry, 2011, 46,

224 P113 THERETICAL STUDY F MULTISTEP MECHAISM F THERMAL FRAGMETATI F -ITR TLUEE E.V. ikolaeva, A.G. Shamov, G.M. Khrapkovskii Kazan ational Research Technological University, Catalisis Department, Kazan, Russia A mechanism which is believed to be involved in thermodistruction of o-nitrotoluene (I) and other nitroarenes bearing hydrogen-containing substituent in ortho-position to nitro group, includes the formation of its aci-form at the first step. At the same time, significant differences in activation enthalpies ( H = E a RT) of thermodistruction of compound I were observed by different authors. Thus, in the temperature interval о С H equals 172,8 kj/mol[4]; о С H = 201,6 3 kj/mol; о С H = 206,2 kj/mol. Results of theoretical investigation of the thermodistruction mechanism of compound I, can be presented as the following scheme: The data on relative enthalpies of formation of transition states of reactions ( H f, enthalpy of formation of o-nitrotoluene was selected as zero) for this scheme provided in the literature suggest that it should terminate at the limiting step of hydrogen atom transfer between two oxygens in the group =()H (process III VI). Possibility of further reactions remained unclear. The investigation of the specified sequence of transformation of o-nitrotoluene by B3LYP/6-31+G(2df,p) demonstrated that this scheme can be realized if isomerization III IV proceeds as a rotation of =()H around С= bond. For this process, H f equals 188 kj/mol. The limiting steps are elimination of water (V VII) or hydroxyl radical (V VI) from 2,1-benzisoxazol- 2(3H)-ole (V), with barriers being equal 193,0 and 204,9 kj/mol, respectively. That is, at lower temperatures, a more probable would be the realization of the process V VII, since for it H f correlates well with experimental estimation of 201,6 3 kj/mol. At higher temperatures, there is an opportunity for elimination of H from compound V (V VI), since for it H f correlates well with experimental estimation of kj/mol. In favor of this conclusion is the systematic character of deviations (1-9 kj/mol decrease) of calculated values of activation enthalpies of primary act and specified steps from experimental data. 1. V.G. Matveev, V.V. Dubihin, G.M. azin, Izv. Acd. auk USSR. Ser. chem., 2, (1978). 2. G.M.Khrapkovskii, A.G.Shamov, E.V.ikolaeva, D.V.Chachkov, Russ.Chem.Rev., 78, 10, (2009). 3. Y. Y. Maksimov, Zh. Phys. Chem., XLIII, 3, (1969). 4. T.B. Brill, K.J. James, Chem. Rev., 93, (1993). 5. W. Tsang, D. Robaugh, W.G. Mallard, J. Phys. Chem., 90, (1986). 6. Y.V. Il ichev, J. Wirz, J. Phys. Chem. A., 104, (2000). 7. S.C. Chen, S.C. Xu, E. Duau, M.C. Lin, J. Chem. Phys. A., 110, (2006). 8. G. Fayet, L. Joubert, P. Rotureau, C. Adamo, J. Phys. Chem. A., 113, (2009). 9. E.V. ikolaeva, D.V. Chachkov, A.G. Shamov, G.M. Khrapkovskii, Vestnik ovgu, 2, 73, (2013). 224

225 P114 PTICAL ACTIVE BIS-IMIE RHDIUM(I) CMPLEXES I TRASFER HYDRGEATI F PRCHIRAL C= BDS L.. indakova, A.V. Khatashkeev,.M. Badyrova, I.A. Ushakov, E.Kh. Sadykov Irkutsk State Technical University, Physical-technical Institute, Irkutsk, Russia Rhodium (1+) complexes with bis-aldimine ligands on the basis of (R,R)-1,2-cyclohexanediamine (1) were tested in the asymmetric transfer hydrogenation of ketones and ketoacids, with isopropanol as hydrogen source under basic conditions. The catalyst:substrate ratio was 1/ Ligands (1а-1с) were synthesized by the condensation reaction of diamine 1 with aldehides: 2- pyridinecarbaldehyde, 2-quinolinecarbaldehyde and 2-thiophene-carbaldehyde, following the scheme:, R - = Rhodium complexes were used as catalysts for this reaction, it was confirmed by 1 Н and 13 С HMR that this complexes were formed in situ from the reaction of [Rh(1,5-CD)Cl] 2 and ligands 1a-1с. TF and T values are higher for ligands that synthesize from 2-pyridinecarbaldehyde (250 h -1 ; 340) and from 2-quinolinecarbaldehyde (109 h -1 ; 170); the lowest values were obtained for bisaldimine based on 2-thiophene-carbaldehyde (16 h -1 ; 43). The excess formation of R-(+)- enantiomer of 1-phenylethanol and R-(-)-methyl mandelate is observed for all Rhodium complexes. But the all used catalytic systems are slightly enantioselective (prior to 20 % of ee), similar result was obtained using Ir - and Ru -bis(oxazoline) catalytic system [1]. [1] Gömez M, Jansat S., Muller G., Bonnet M. C., Breuzard J. A.J., Lemaire M. J. rganomet. Chem, 2002, 659,

226 P115 STRUCTURAL AALYSIS F IDIE ADDUCTS WITH HETERARMATIC -XIDES V.V. Romanov 1, Y.P. izhnik 1, A.V. Ryzhakov 2, L.L. Rodina Petrozavodsk State University, Petrozavodsk, Russia 2 - Karelian Research Center RAS, Petrozavodsk, Russia 3 - St. Petersburg State University, St. Petersburg, Russia Heteroaromatic -oxides contain two potential donor centers capable to interact with Lewis acids such as halogen bond donors: -system of the aromatic rings and the oxygen atom of -oxide group. According to the HSAB principle, the iodine as a soft Lewis acid might interact on both donor centers, however the literature and our IR-spectroscopy data unambiguously indicate the oxygen atom as a donor center. Yet a half-century ago T. Kubota [1] questioned the exact geometry of iodine adducts of -oxides due to potentially different hybridization types of oxygen atom. Actually, owing to an ambivalent character of the group in the heteroaromatic -oxides, the oxygen atom s hybridization might be characterized by the two extreme cases sp 3 or sp 2. Single X-ray data obtained by us for the adducts of iodine with pyridine, 4-methylpyridine and 4- chloroquinoline -oxides have clearly demonstrated the sp 3 -character of the oxygen atom in the complexes and the absence of any -interaction. In the both cases for pyridine -oxides, the structure of the adducts includes infinite quasi one dimensional chains of alternating D and A moieties: ( I I I I ). In the case of the adduct of 4-chloroquinoline -oxide with iodine (see the picture), the individual adduct molecule may be distinguished within the crystal lattice. To estimate the possibility of existing different conformations of the adduct (sp 3 or sp 2 ), on the base of its crystal structure the energy profile of the structure was calculated in Hyperchem program as the dependence of the potential energy on the dihedral angle (I I ) (quinoline ring): Two distinct barriers have been observed: at 0 o ( E = 357 Kcal/mol, corresponds to the structure where iodine is in a close proximity to H8), and 180 o ( E = 3.7 Kcal/mol, iodine is in a close proximity to H2). The real X-ray structure (dihedral angle 117 o, ( E = 0.25 Kcal/mol) is similar to the calculated conformer (dihedral angle 131 o, ( E = 0 Kcal/mol)). btained data indicate that potential sp 2 -stereoisomers are not favorable energetically due to probably the sterical factors and should not be observed at least in the case of strong adducts with bulky Lewis acids. [1] T. Kubota // J. Amer. Chem. Soc (3). P

227 P116 CPPER CATALYZED CYCLPRPYL-ALLYLIC RIG-PEIG TRASFRMATIS F GEM-CHLRFLUR- AD GEM- BRMFLURCYCLPRPAES. PREPARATI F 2- FLURALLYL HALIDES M.A. ovikov,.v. Volchkov, M.B. Lipkind,.M. efedov. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation Cyclopropyl-allylic ring-opening transformation of gem-chlorofluoro- and gem-bromofluorocyclopropanes widely available by carbene cyclopropanation of corresponding alkenes is an attractive tool for preparation of 2-fluoroallylic compounds that are known to possess a wide range of biological activities. Ability of copper(i) compounds to catalyze cyclopropyl-allylic isomerization of gem-chlorofluoroand gem-bromofluorocyclopropanes was found and an effective route to 2-fluoroallyllic chlorides and bromides was developed. R 1 R 3 C F X R 1 F X R 3 C u X /M ec R 1 F X R 2 R 4 R 2 R 4 o r ( H C )C u X /d io x an e C R 2 R 3 R 4 X = C l, B r; R 1 -R 4 = H, C H 3, -(C H 2 ) n - (n = 2-4 ), P h, -C H = C H 2, c-c 3 H 5, C l; Thus, from alkyl-, aryl, chloro substituted gem-chlorofluoro- and gem-bromofluorocyclopropanes, their bicyclic and spiro-substituted derivatives, in presence of CuX or (HC)CuX (HC - heterocyclic carbene) in MeC or 1,4-dioxane at elevated temperatures corresponding 2- fluoroallyllic chlorides and bromides could be prepared. In the case of vinyl substituted gemchlorofluorocyclopropane 5-chloro-2-fluoropenta-1,3-diene forms as a major product. Isomerization of gem-chlorofluoro-1,1 -bi(cyclopropane) proceeds via successive opening of both cycles leading to 6-chloro-2-fluorohexa-1,3-diene as an only product. References 1). V. Volchkov, M. A. ovikov, M. B. Lipkind, and. M. efedov, Mendeleev Commun., 2013, 23, 19 21; 2) M. A. ovikov,. V. Volchkov, M. B. Lipkind, and. M. efedov, Russ. Chem. Bull., 2013, 62,

228 P117 DESIG, SYTHESIS AD BILGICAL EVALUATI F P- GLYCPRTEI IHIBITRS FR MDULATI AD PREVETI F MULTIDRUG RESISTACE M. Sagnou 1, X. Alexiou 1, E.S. Kolotova 2, A.A. Shtil 2, A.A. Zeifman 3, I.J. Titov 3,.V. Stroganov 3, V.V. Stroylov 3, I.V. Svitanko 3, F.. ovikov 3, G.G. Chilov Demokritos ational Research Center, Greece 2 - Russian Scientific ncology Center RAS 3 -. D. Zelinsky institute of organic chemistry, Russia Multidrug resistance (MDR) mediated by P-glycoprotein (one of ATP-binding cassette (ABC) transporters) through efflux of antineoplastic agents from cancer cells is a major obstacle to successful cancer chemotherapy. The inhibition of P-glycoprotein (P-gp) is thus a logical approach to circumvent MDR. There has been intensive research effort to design and develop novel inhibitors for the P-gp and other ABC transporters to achieve this goal. Complex in silico P-gp inhibition model was developed in the present study using the pharmacophore ensemble/support vector machine scheme (to take into account the promiscuous nature of P-gp), molecular docking and molecular dynamics approach (to predict ligand binding pose in huge P-gp hydrophobic cavity) and free energy perturbation methods (FEP, to accurate estimation of ligand-binding affinities). Two series of novel P-gp inhibitors (based on curcumine scaffold) was designed, synthesized and evaluated in doxorubicin accumulation and cytotoxicity tests on chronic myeloid leukemia cell line К562/Dox with MDR phenotype. During the first round of optimization we discovered novel P-gp inhibitors that bind to the active site of the enzyme and have activity comparable to clinical P-gp blocker verapamil. We showed that that hydrogen bonds with residues T837 and Q737 and hydrophobic and stacking interactions with residues P770, Y307 and P994 play significant role in ligand binding. We demonstrated that for correct predictions of relative binding energy by FEP it is necessary to carry out an explicit account of the solvent, since the bridging water molecules significantly contribute to the energy of formation of the protein-ligand complex. In the second round of optimization we discovered P-gp inhibitors that were to verapamil and comparable with P-gp inhibitors in clinical trials. We demonstrated that these compounds do not exhibit the toxicity at concentrations up to 50 um and have more than 100-fold lower IC50 in doxorubicin cytotoxicity tests on К562/Dox with MDR phenotype 228

229 P118 SELECTIVE HYDRGEATI F USATURATED ALDEHYDES THE CMPSITE Pt-BASED ACATALYSTS. A QUATUM CHEMICAL STUDY A.I. khapkin 1,.B. Gadzhiev 1, A.E. Masunov 2, S. Kunz 3, M. Bäumer 3, S.K. Ignatov I. Lobachevsky State University of izhny ovgorod, Chemistry Department, izhny ovgorod, Russia 2 - University of Central Florida, Chemistry Department, rlando, USA 3 - University of Bremen, Institute for Applied and Physical Chemistry (IAPC), Bremen, Germany Selective hydrogenation of unsaturated aldehydes to alcohols is a key process in fabrication of fragrance components for the modern cosmetology and perfume industry. Since the selective oxogroup hydrogenation is thermodynamically unfavorable due to the presence of the C=C bond, the industrial process is indirect, complicated, and expensive. Recently, a novel type of catalyst was proposed that shows enhanced selectivity towards unsaturated alcohols. It is using metal-oxide supported Pt-nanoparticles with chemically modified surface. In a present work, the elementary steps of such a catalytic reaction, i.e., propenal and croton aldehyde hydrogenation, were studied within the cluster models of Pt surface using the DFT quantum chemical calculations (BLYP and PBE density functionals in conjunction with the CREBS or LAL2DZ pseudopotentials for Pt atoms and 6-31G(d,p) basis set for the remaining atoms). The clusters Pt 8, Pt 13, and Pt 25 consisting of two layers of Pt atoms were used as models for the Pt nanoparticle surface. The diameter of the Pt 25 cluster is about 12 Å which is close to the size estimated for the experimentally studied Pt nanoparticles (18±3Å) [1]. The different spin states of the clusters were considered (spin multiplicity up to 11). The adsorption of reagents (H 2 and aldehydes) and the organic ligands working as orienting agents ensuring the reaction selectivity (BuSH, Bu = n-c 4 H 9 ) were studied as initial steps of the catalytic process. The various kinds of adsorption were studied: (1) physical adsorption of H 2 on different sites of Pt n clusters; (2) dissociative chemisorption of H 2 resulting in the Pt-adsorbed H atoms; (3) chemisorption of ligands forming the Pt n -SBu structures and the neighboring SBu/H adsorbed pairs; (4) aldehyde adsorption on the neat Pt surface and the surface partially occupied by the H atoms and the SBu and SBu/H groups. For all these pre-reaction surface complexes, the molecular structures, adsorption energies, and vibrational frequencies were studied. It was found that the ground state of the Pt 25 clusters is the quintet one with the typical spread of energies in lower spin states (M=1,3,5, and 7) of about 3 kcal mol -1. The H 2 physical adsorption energy is about kcal mol -1 depending on the adsorption site. The dissociative adsorption energy of H 2 was estimated to be 5-9 kcal mol -1 which is in reasonable agreement with experimental values (~16 kcal mol -1 )[2]. At the same time, the SBu group formation energy was estimated as kcal mol -1 depending on the adsorption site. Their estimated surface coverage of about 4/9 monolayer is in reasonable agreement with the experimentally observed dependence of hydrogenation kinetics on the surface coverage [1]. The kinetic barriers of the surface migration of adsorbed H atoms and various hydrogenation pathways are discussed on the basis of the different theoretical estimates. 1. L. Altmann, S. Kunz, M. Bäumer, J. Phys. Chem. C 2014, 118, P.R. orton, J.A. Davies, T.E. Jackman, Surf. Sci., 1982, 121, The work was partially supported by the Russian Foundation for Basic research (project o ). BG and AI are thankful to DAAD for the travel grants support. 229

230 P119 MR DIFFERETIATI F CHIRAL ALCHLS AD AMIES USIG SELEIUM-BASED CHIRAL PRBES.V. rlov, V.P. Ananikov Zelinsky Institute of rganic Chemistry RAS, Russia, Moscow, Leninsky pr. 47, Modern MR spectroscopy is a powerful tool for structure elucidation of complex organic molecules including natural products 1. An important issue in this field is analysis of complex mixtures of chiral compounds and determination of enantiomeric composition of each individual molecule. Utilization of chiral auxiliary reagents allows to efficiently differentiate enantiomers in MR spectra 2. Besides, continuous progress in development of chiral auxiliaries and derivatization protocols made it possible to obtain diastereomers suitable for MR analysis within minutes directly in MR tube excluding isolation and purification steps 3. evertheless analysis of mixtures of several chiral compounds is still a complicated task 4. Recently we have developed simple synthetic routes to several selenium-based chiral probes which readily react with chiral alcohols and amines directly in an MR tube (Scheme 1, left) followed by determination of their enantiomeric composition using 77 Se MR spectroscopy 5. In this case only signals of selenium-containing diastereomers formed are observed in the spectra thus simplifying assignment procedure. Scheme 1. DCC-promoted "in tube" derivatization of chiral alcohols and amines with chiral probes R-ArSePA (left) and examples of spectral data - structure relationship using R-(4- chlorophenylselanyl) propionic acid (right). ow we have revealed that the diastereomers formed can be efficiently differentiated in 77 Se MR spectra depending on the nature of substituents at stereogenic center of analyzed chiral aclohols and amines (Scheme 1, right). This observation gives possibility to perform preliminary structure elucidation in several minutes and to analyse complex mixtures using a single 1D MR experiment. Scope and limitations of this approach to various chiral alcohols and amines will be presented in the poster. Acknowledgments: This work was supported by RFBR (project o ). 1. Breton, R. C.; Reynolds, W.F. at. Prod. Rep. 2013, 30, Wenzel, T. J. Top. Curr. Chem. 2013, 341, 1. Chem. Rev. 2012, 112, ovoa-carballal, R.; Fernandez-Megia, E.; Jimenez, C.; Riguera, R. at. Prod. Rep. 2011, 28, rlov,. V.; Ananikov, V. P. Chem. Commun. 2010, 46,

231 P120 EW LIFE FR LD REACTI. SYTHESIS F THIAZLIDIES VIA REGISELECTIVE ADDITI F USYMMETRIC THIUREAS T MALEIC ACID DERIVATIVES A.S. Pankova, M.A. Kuznetsov Saint Petersburg State University, Insitute of Chemistry, Saint Petersburg, Russia Thiazolidine derivatives and, in particular, thiazolidinylacetic acids are highly valuable scaffolds for medicinal and bioorganic chemistry as can be exemplified by a central penicillin core that contains fused -lactam and thiazolidine rings. Various substituted thiazolidines feature exclusively broad range of biological activities that warrants a constant interest in preparing new thiazolidines and studying their properties. Addition of thiourea derivatives to maleic anhydride or maleimides is used to get a rich functionalized thiazolidinylacetic acid framework. This reactions is classical, but at the same time many questions concerning regioselectivity in case of unsymmetric thioureas remained unclear and there were problems to be solved. Some controversial data and surprising results can be found in the literature and therefore we decided to thoroughly investigate factors governing the regioselectivity of this process. We have shown that addition of -aryl- -ethyl(or methyl)thioureas to -arylmaleimides proceeds regioselectively providing 2-(3-ethyl(methyl)-2-arylimino-4-oxo-1,3-thiazolidin-5-yl)-arylacetamides in good yields. It is applicable for a wide range of substituents in aromatic rings and the product selectivity does not depend on the solvent used. A remarkable dependence of the reaction regioselectivity on the solvent polarity was revealed with more sterically hindered alkyl thioureas. In nonpolar benzene 3-alkyl-2-arylimino-4-oxo-1,3-thiazolidines are formed preferentially, whereas in polar isopropyl alcohol and acetonitrile the reaction regioselectivity changes in favor of 2-alkylimino-3-aryl-4-oxo-1,3-thiazolidines. In the case of the most bulky -tert-butyl- -phenylthiourea, the isomer with exo-cyclic position of an alkyl group is formed exclusively. At the same time addition of sterically hindered -alkyl- -arylthioureas to maleic anhydride leads only to 3-alkyl-2-arylimino-4-oxo-1,3-thiazolidinylacetic acids independent of the solvent used. We have unambiguously established the structures of all obtained thiazolidines (some of them using X-ray data) and demonstrated the utility of the 15-1 H HMBC spectroscopy for their unequivocal assignment. Authors thank the Russian Scientific Fund for a research grant no

232 P121 MECHAISTIC STUDY F Cu 2 AD Cu-CATALYZED C S CRSS CUPLIG REACTI Y.S. Panova 1, V.P. Ananikov Saint-Petersburg State University Institute of Chemistry, Russia, Petrodvorets, Universitetsky pr D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Russia, Moscow, Leninsky pr. 47 C-S cross-coupling is a valuable synthetic tool to prepare a diversity of sulfur derivatives with high yields [1,2]. In spite of various synthetic applications, the mechanism of C-S cross-coupling was not clearly resolved. Catalytic reactions mediated with Cu and Cu 2 nanoparticles represent a substantial challenge in this regard. In order to have a better insight of the reaction pathways, detailed FE-SEM, ESI-MS and MR studies were carried out. Ligand-free copper oxides (I, II)-catalyzed reactions of thiophenol with 4- iodotoluene were chosen as a model reaction. The role of copper centers on the surface of the nanoparticles and in solution was studied and compared to reported in the literature reaction pathways. It is interesting to note, DFT calculations revealed that strongly polar solvent (like DMS) facilitates the formation of the anionic active species [Cu(SPh) 2 ] - [3]. This type of intermediates is favored for halogen atom transfer mechanism as its activation energy barrier much lower (33.2 kcal/mol), then the activation energy barrier of the most often suggested oxidative addition mechanism (41.3 kcal/mol), according to theoretical study [3]. Based on calculations and experimental data we will discuss the following catalytic pathways: 1) generation of [Cu(SPh) 2 ] - complex by reaction of thiophenol with the base and copper oxides; 2) iodine atom transfer from 4-iodotoluene to Cu-center to form the [Cu(SPh)I] - intermediate and phenyl radical; 3) attack by phenyl radical at S atom of Ph-thiolate affording the formation of coupling product. It is noteworthy, that in the absence a base, intermediate [CuI 2 ] - was observed by ESI-MS analysis. References [1] S. Ganesh Babu, R. Karvembu Tetrahedron Lett., 2013, 54, [2] S.-W. Cheng, M.-C. Tseng, K.-H. Lii, C.-R. Leec, and S.-G. Shyu Chem. Commun., 2011, 47, [3] S.-L. Zhang, and H.-J. Fan rganometallics, 2013, 32, Acknowledgment P.Y. acknowledges Saint-Petersburg State University for postdoctoral fellowship ( ). 232

233 P122 TRASFRMATIS F CYCLIC RGAIC PERXIDES I THE PRESECE F TRASITI METALS Z.Y. Pastukhova 1, I.A. Yaremenko 1, L.G. Bruk 2, A.. Terent ev D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences 2 - Lomonosov Moscow State University of Fine Chemical Technologies Currently, organic peroxides are produced by dozens of the largest chemical companies in a largetonnage scale. Peroxides are the main source of free radicals in chemical practice. They are widely used to initiate radical including chain-radical processes, especially in the polymer manufacture. In the past decades, the chemistry of organic peroxides has attracted considerable attention from physicians and pharmacologists due to the detection of these compounds high antimalarial, anthelminthic and antitumor activities. Thermal instability of peroxides, because of the presence of weak - bonds, leads to decomposition at normal or elevated temperatures. Transition metals (Fe, Сu, Мn, Со, Сr) and their salts are effective catalysts of decomposition. Usually decomposition of organic peroxides is nonselective process. Decomposition reactions are not limited by the only homolytic decomposition of - bond resulting in a complex product mixture is generated. In our work we found the selective transformations of cyclic organic peroxides in the presence of transition metals (Scheme 1). Scheme 1. Transformations of Cyclic rganic Peroxides? M n+?? This work is supported by RFBR Terent ev A.., Yaremenko I.A., Chernyshev V.V., Dembitsky V.M., ikishin G.I. // J. rg. Chem. 2012, 77, Terent'ev A., Yaremenko I.A., Vil' V.A., Dembitsky V.M, ikishin G.I. // Synthesis. 2013, 45 (2), Ingram K., Yaremenko I.A., Krylov I.B., Hofer L., Terent'ev A.., and Keiser J. // J. Med. Chem. 2012, 55 (20),

234 P123 EATISELECTIVE HYDRLYSIS F 3-HYDRXY-1,4- BEZDIAZEPI-2-E ESTERS BY PIG LIVER MICRSMES V.I. Pavlovsky 1, E.A. Shesterenko 1, I.I. Romanovska 1,.V. Sevastyanov 1, T.A. Yurpalova 1, S.A. Andronati 1, V.Ch. Kravtsov A.V. Bogatsky Physico-chemical Institute, ational Academy of Sciences of Ukraine, Lustdorfska dor., 86, dessa, Ukraine 2 - Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Republic of Moldova The configuration of chiral biologically active compounds plays an important role in processes of their biotransformation and binding with biomembranes. Methods of asymmetric synthesis and resolution of enantiomers are fraught to difficulties, thus development of economical preparative biotechnological methods of enantiomers resolution is prospective. Carboxylesterase (EC ) is the most studied enzyme, which catalyze the enantioselective hydrolysis of a wide range of acyclic, carbocyclic and heterocyclic compounds. But the number of publications, devoted to the enantioselective hydrolysis of benzodiazepine derivatives, which clinical effects include anxiolytic, anticonvulsant and hypnotic effects, muscle relaxation is quite limited. The aim of the present work was the development of a method of the enantioselective hydrolysis of 3- hydroxy-1,4-benzodiazepin-2-one esters by pig liver microsomes and investigation of S-enantiomers binding affinity for central benzodiazepine receptors. Microsomal fraction was isolated by the low speed centrifugation method in the presence of Ca 2+ ions. Protein yield was 38.0 mg/g of liver tissue and esterase activity was U/mg protein. The method of enantioselective hydrolysis of 1-unsubstituted-(1), 1-methyl-(2), 1-ethyl-(3) 3-acetoxy-7- bromo-5-phenyl-1,2-dihydro-3h-1,4-benzodiazepin-2-ones using pig liver microsomal fraction was developed (esterase activity 130- U/cm 3 ; ph 7,0; t 37 ºC; τ 2,5 h; DMS concentration 40 % (v/v)). Enantiomers of 3-hydroxy-1,4-benzodiazepin-2-one esters were purified by silica gel column chromatography. Enantiomeric excesses of substrates (ee s ) were determined by HPLC using Shimadzu LC- 8A pump with a chiral column ChiraDex. It was shown, that the products of the reaction 1-unsubstituted- (4), 1-methyl-(5), 1-ethyl-3-hydroxy-7-bromo-5-phenyl-1,2-dihydro-3H-1,4-benzodiazepin-2-ones (6) underwent racemization during hydrolysis and subsequent isolation, what is consistent with the literature data [1]. The S-enantiomers of three substrates 1S-3S were obtained with ee s >97 % and yields %, their absolute configurations were determined by X-ray crystallography (fig.). 1S 2S 3S(a) 3S(b) Fig. RTEP view of molecular structure of 1S, 2S, and two conformers in the structure 3S (a and b) illustrates their absolute configuration. 20 Values of specific rotation of 1S-3S were º, º, º (c = 1.0, CHCl D 3), respectively. With a help of the radioligand binding methods, affinity of S-enantiomers 1S-3S and racemates 1-3 for the CBR of rat brain was determined and values of IC 50 were evaluated. It was shown, that the S-enantiomers 1S-3S are times more potent ligands of CBR than the corresponding racemates 1-3. References: 1. swald P., Desmet K., Sandra P. et al, 2002 Determination of the enantiomerization energy barrier of some 3- hydroxy-1,4-benzodiazepine drugs by supercritical fluid chromatography. J. Chromatogr. B. 779,

235 P124 A SIMPLE TECHIQUE FR PRDUCIG PALLADIUM APARTICLES CARB SUPPRT AS CATALYST FR CRSS-CUPLIG REACTIS E.. Pentsak, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry RAS, Moscow, Russia Recently, much attention has been paid to carbon materials, modified by metal nanoparticles, due to increasing interest in using of such systems in catalysis, material science optics and electronics. Successful application of palladium nanoparticles supported on carbon materials was facilitated many organic synthesis procedures. Efficiency and selectivity of these catalysts was determined by such characteristics as particles size, the uniformity of their distribution on the support surface and the range of particle size distribution. We have previously shown that the labile behavior in solution and the tendency to form palladium clusters are inherent in Pd 2 dba 3 complex [1]. Thus, we were able to cover carbon material by nanoparticles with optimum sizes and high monodispersity under mild conditions without the need of stabilizers and reducing agents, using easily available Pd 2 dba 3 complex as a precursor of palladium. In this study, we found that the variation of temperature and concentration of solution allowed tuning of coverage density of the supported nanoparticles, as well as control of diameter of the nanoparticles from 2 to 15 nm. This procedure was found scalable and well reproducible. Dispersion values of the nanoparticles sizes usually did not exceed 1-2 nm. Kinetics of the process was investigated by nuclear magnetic resonance spectroscopy MR and scanning electron microscopy (FE-SEM). Study of deposition process by FE-SEM showed that the average particles size was stabilized quickly during the coating process. The particles size depended on the conditions of the process, while the increase of the coating density occurred gradually until complete consumption of the Pd precursor. The catalytic activity of prepared palladium nanoparticles supported on graphite has been studied utilizing model Suzuki and Heck reactions. The catalyst prepared by our method showed high efficiency for this type of reactions, 100% conversion of the Heck and Suzuki reactions was reached only in a few hours at low catalyst loadings ( mol %). [1] Zalesskiy S. S., Ananikov V. P. // rganometallics, 2012, V. 31, P

236 P125 SELECTIVE CLEAVAGE F GLYCSIDIC LIKAGES USIG SLVLYSIS WITH AHYDRUS TRIFLURACETIC ACID S.. Senchenkova, A.V. Perepelov, A.V. Filatov, A.S. Shashkov, Y.A. Knirel.D.Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia A common approach in structural studies of polysaccharides is the selective cleavage of glycosidic linkages to give oligosaccharide fragments, which usually show better-resolved MR spectra than the parent polymer and are readily amenable to MS analysis. ne of the methods useful for this purpose is solvolysis with strong acids. For instance, solvolysis with anhydrous HF has been used in structural analysis of carbohydrates since early 1980s, and later trifluoromethanesulfonic (triflic) acid was introduced. However, these reagents have some disadvantages; e.g. HF handling requires special equipment, triflic acid is expensive, and both are highly hazardous. In search for a better solvolytic agent, we tested anhydrous CF 3 C 2 H in selective cleavage -polysaccharides of medically important bacteria Escherichia coli and Enterobacter cloacae and found it to be useful and convenient. CF 3 C 2 H split selectively the α1 2- and α1 3-rhamno- and -fuco-pyranosidic linkages as well as the HexpAc-(1 4)-Manp linkage, whereas other linkages were not affected. Below are structures of the cleaved -polysaccharides (68 at 50 C for 16 h; all others at 40 C for 5 h) with the glycosidic linkages sensitive to CF 3 C 2 H shown in rectangles. 236

237 P126 СRSS-CUPLIG F TEREPHTHALITRILE DIAI AD ARMATIC ITRILE RESULTIG I SUBSTITUTED DICYABIARYLS R.Yu. Peshkov 1, E.V. Panteleeva 1, V.D. Shteingarts ovosibirsk State University, ovosibirsk, Russia Vorozhtsov ovosibirsk Institute of rganic Chemistry, ovosibirsk, Russia Cyanobiaryls have a wide area of practical utilization in technology (polymers, semiconductors, LED) as well as in medicine [1]. Modern approaches to their synthesis are based on manifold cross-coupling reactions of preactivated arenes catalyzed by transition metals. We suggest a concise and inexpensive non-catalytic approach applying terephthalonitrile dianion 1 as cyanoarylating reagent for neutral aromatic nitriles. It was found that 1, generated by terephthalonitrile reduction with alkali metal in liquid ammonia, undergoes cross-coupling with benzonitrile as well as 2- and 3- cyanobiphenyls providing 4,4`-dicyanobiphenyl and dicyanoterphenyls [2]. Present work is aimed on broadening the scope of neutral substrates applicable for such type of cross-coupling and study of its mechanism by revealing electronic and structural factors governing regioselectivity and efficiency of the reaction. For the purpose we varied the nature of substrate by introduction of an extra substituent into benzonitrile (Me, Me, F, Cl, Br) as well as by alteration of aromatic moiety. (cyanonaphthalenes, 9-cyanoanthracene, 4-cyanopyridine). Besides nitriles, electron-deficient arenes: ethylbenzoate, 3-methylbenzophenone and nitrobenzene were tested. Also experimental and quantum-chemical modeling of possible reaction pathways were performed. We found out that benzonitriles substituted with o-, m-me, -Me and -F, both cyanonaphthalenes and 9- cyanoanthracene undergo coupling with 1 providing subsequent cyanobiaryls (scheme). Towards all other substrates 1 acts as reducing reagent. The regularities revealed are interpreted in terms of the reaction scheme with the intermediacy of the charge-transfer complex 2 between 1 and cyanoarene [2], which further transforms into dimeric dianion 3 either by heterolytic pathway or by successive single electron transfer and recombination of primary generated radical anions. Subsequent decyanation of 3 forms long-living monoanion 4 capable to be converted into cyanobiarylic product either through oxidation or alkylation. C 2- C 1 + C C 2M + ArX 2- H 3 C M: Li, a, K X: H; 2-, 3-CH 3 ; -CH 3 ; -F C 2- C ET C C * in-cage recombination X C X C X CTC primary RA-pair 2 heterolytic pathway (S Ar) ArX: C C X Bu C X C C C F X F F F F C F F C C F F C C F F C C C C C C C C X C -C - C C C 3 4 X X C C X Bu C C [] AlkBr -Br - C C C Alk C C C X X -H + -C - Alk C C X cyanobiaryle yield 14-90% The financial support of the CMSD of RAS (the project o 2.6) is acknowledged. [1] Corbet, J.-P., Mignani, G. Chem. Rev., 2006, 106, [2] a) Panteleeva, E.V. et al., Eur. J. rg. Chem., 2005, 2558; b) Panteleeva, E.V. et al., ARKIVC, 2011, viii, 123. C C C 237

238 P127 REARRAGEMET F CYCLIC 9-MEMBERS Si-PERXIDES R.A. Pototskiy 1, R.A. ovikov 2, A.. Terentev 1, G.I. ikishin 1, A.V. Arzumanyan D. Zelinsky Institute of rganic Chemistry, Laboratory for Studies of Homolytic Reactions, Moscow, Russia 2 -. D. Zelinsky Institute of rganic Chemistry, Laboratory of Carbene Chemistry and Small- Sized Cyclic Compounds, Moscow, Russia Among organic peroxides, compounds with Si moiety are less known than their carbon analogues. As the result there are few examples of reaction of silicon containing peroxides in literature. In the previous works we reported about successful synthesis of different silicon containing cyclic peroxides [1,2]. ow we focused on investigation of treatment of such compounds with different reducers and Lewis acids (LA). S i R R ' S i It has been shown that treatment of the cyclic Si-peroxides with different reducers leads to contraction of peroxide cycle on two oxygen atoms. otably each peroxide group lost one oxygen atom giving earlier unknown silylprotecting diols. Reaction was carried out in diethyl ether medium at ambient temperature in the presence of 3-fold access of a reducer. The best results were reached with triphenylphosphine. Yield of products were 60 to 75%, depending on structure of starting substance. Such products may be used as building blocks bin different bioactive compounds. Treatment of bis-sililperoxides under LA action was studied. The reaction was carried out in different reaction media with 2-fold excess of LA (SnCl 4, TiCl 4, AlCl 3 ). It has been established that the way of reaction depends on nature LA catalyst. For example, formation of lactones yield of 80 95% was observed (Bayer-Villiger-like reaction) in the presence of SnCl 4. In case of TiCl 4 the combination of a regrouping and formation of an appropriate ketone was observed; with AlCl 3 reaction did not flow past. Summary, in this work chemical reactions of cyclic Si-peroxide compounds have been investigated. rganic silicon peroxide compounds can enter various reactions leading to formation of lactones, diols with a trialkylsilyl group, depending on reaction conditions that point to their high synthetic potential. References: [1] Arzumanyan A.V., Terent ev A.., ikishin G.I. et.al. rganometallics, 2014, 33, [2] Platonov M.M., Terent ev A.., ikishin G.I. et.al. J. rg. Chem., 2008, 73,

239 P128 EFFICIET E-PT SYTHESIS F DIVERSE BEZ[C[CHRMEE- 6-ES BY BASE-PRMTED CASCADE REACTIS T.. Poudel, Y.R. Lee School of Chemical Engineering, Yeungnam University, Gyeongsan , Republic of Korea Molecules bearing benzo[c]chromen-6-one and its derivatives are extensively distributed in nature. 1 Some of these molecules exhibit biologically and pharmacologically important antitumor and antibiotic activities, 2 promote endothelial cell proliferation, and inhibit oestrogene receptor growth activities. 3 Due to the importance of these biological and pharmacological activities, several synthetic methods have been devised to produce benzo[c]chromen-6-one derivatives. f these methods, the most useful method involves a Suzuki-Miyaura cross-coupling reaction followed by metal or Lewis acid mediated lactonization of ester and methoxy groups. 4 Recently, a new reaction involving a microwave-assisted Diels-Alder reaction betwee 4-cyanocoumarin and 1-oxygenated dienes followed by elimination and aromatization with a strong base was also described. 5 However, these synthetic approaches included two-step reactions and required purification of the intermediate. In addition, the starting materials used for these transformations were synthesized from corresponding materials in two or more steps. Thus, a mild, general, and efficient one-pot synthetic route for benzo[c]chromen-6-one derivatives using inexpensive catalysts and reagents is still in demand, especially a route that allows minimization of the steps and access to diverse products. We present herein a novel one-pot synthesis of a variety of benzo[c]chromen-6-one derivatives using Cs 2 C 3 -promoted reactions of substituted 2-hydroxychalcones and β-ketoesters. These reactions involved cascade Michael addition/ intramolecular aldol/ oxidative aromatization/ lactonization and provided an efficient synthetic route for the production of biologically interesting novel benzo[c]chromen-6-one molecules bearing several different substituents on benzene rings. As an application of this methodology, several synthesized benzo[c]chromen-6-ones were transformed into highly functionalized novel terphenyls. References: 1. (a) Ya. L. Garazd, A. S. gorodniichuk, M. M. Garazd andv. P. Khilya, Chem. at. Compd., 2002, 38, 424; (b) K. Ishiguro, M. Yamaki, M. Kashihara, S. Takagi and K. Isoi, Phytochemistry,1990, 29, 1010; (c) H. Abe, K. ishioka, S. Takeda, M. Arai, Y. Takeuchi and T. Harayama, Tetrahedron Lett.,2005,46, (a) T. Hosoya, E. Takashiro, T. Matsumoto and K. Suzuki, J. Am. Chem. Soc.,1994, 116, 1004;(b) C. A. James and V. Snieckus, Tetrahedron Lett.,1997, 38, (a) J. M. Schmidt, G. B. Tremblay, M. Page, J. Mercure, M. Feher, R. Dunn-Dufault, M. G. Peter and P. R. Redden, J. Med. Chem., 2003, 46, 1289;(b) J. Pandey, A. K. Jha and K. Hajela, Bioorg. Med. Chem.,2004, 12, (a) Q. J. Zhou, K. Worm and R. E. Dolle, J. rg. Chem.,2004, 69, 5147; (b) G. J. Kemperman, B. Ter Horst, D. Van de Goor, T. Roeters, J. Bergwerff, R. Van der Eem and J. Basten,Eur. J. rg. Chem.,2006, 14, M. E.Jung and D. A. Allen, rg. Lett., 2009, 11,

240 P129 PRACTICAL SYTHESIS F 1,2,4-THIADIAZLES VIA` CPPER-MEDIATED HM-CUPLIG F THIAMIDES Y.-D. Sun, C.-R. Qi, H.-F. Jiang South China University of Technology, College of Chemistry & Chemical Engineering, Guangzhou, P. R. China Thiadiazoles are regarded as an important class of five-membered heterocycles for many bioactive molecules. ne general method for the preparation of 1,2,4-thiadiazoles containing the same groups in 3- and 5-positions was oxidative dimerization of the corresponding thioamides using oxidizing agents. ne the other hand, the transition metal-mediated oxidative transformations to construct heterocycles have attracted great interest over the past decade. In particular, copper salts have been successfully applied in the formation of C-hetero or hetero-hetero bonds, which exhibit great potential for the construction of various heterocycles. n the basis of our recent developed Cucatalyzed method for synthesis of heterocycles 1-5 and increasing interest of oxidative cross-coupling reactions of two nucleophiles, herein, we disclose a novel method for 3,5-disubstituted 1,2,4- thiadiazoles via copper(ii)-mediated homo-coupling of thioamides involving C- and -S bond formations (Scheme 1). Scheme 1. Synthesis of 1,2,4-thiadiazoles References 1. Huang, L.; Jiang, H.; Qi, C.; Liu, X. J. Am. Chem. Soc. 2010, 132, Li, X.; Huang, L.; Chen, H.; Wu, W.; Huang, H.; Jiang, H. Chem. Sci. 2012, 3, Gao, Y.; Yin, M.; Wu, W.; Huang, H.; Jiang, H. Adv. Synth. Catal. 2013, 355, Zeng, W.; Wu, W.; Jiang, H.; Huang, L.; Sun, Y.; Chen, Z.; Li, X.; Chem. Commun. 2013, 49, Sun, Y., Jiang, H.; Wu, W.; Zeng, W.; Wu, X. rg. Lett. 2013, 15,

241 P130 HIGHLY EFFICIET SYTHESIS F TERTIARY α-hydrxy KETES VIA C 2 -PRMTED REGISELECTIVE HYDRATI F PRPARGYLIC ALCHLS H.-T. He, C.-R. Qi, H.-F. Jiang South China University of Technology, College of Chemistry & Chemical Engineering, Guangzhou, P. R. China -Hydroxy ketones have attracted tremendous interest in biologically active natural product research and synthetic chemistry. However, few of methodologies could be applicable for efficient hydration of propargylic alcohols to form -hydroxy ketones except the Kucherov reaction using mercury(ii) salts as catalysts. A wide range of transition metals including Pd, Pt, Fe, Au, Ag, Ir and Ru have been investigated for the hydration of alkynes, however, these catalytic systems either showed low activity or led to side reactions such as Meyer-Schuster and Rupe rearrangements. Therefore, the development of novel processes for the hydration of propargylic alcohols to produce -hydroxy ketones with high efficiency is highly desirable. Using C 2 as the feedstock, a great deal of work in many different fields, has been undertaken to produce cyclic carbonates. In our previous work 1, 2, we found that secondary amine was able to attack the carbonyl group of the α-methylene cyclic carbonate to give the ring-opening product. Recently, we set out to study whether water was capable to proceed the nucleophilic attack instead of the secondary amines to furnish useful -hydroxy ketone derivatives (Scheme 1). Scheme 1 References [1] Qi C.; Jiang, H. Green Chem., 2007, 9, [2] Qi C.; Huang, L.; Jiang, H. Synthesis, 2010, 9,

242 P131 UEXPECTED DIRECT CVERSI F FUSED 1,2,5- SELEADIAZLES IT 1,2,5-THIADIAZLES L.S. Konstantinova, E.A. Knyazeva,.A. Rakitin.D. Zelinsky Institute of rganic Chemistry RAS Fused 1,2,5-thiadiazoles have attracted much attention because of their interesting chemical properties and various possibilities for use as antibacterial and antiviral agents, agrochemicals and as π-type building blocks for organic electronics, particularly for both low- and high-molecular organic light-emitting diodes (LEDs). 1 Recently 1,2,5-thiadiazole derivatives were recognized as efficient electron acceptors and successfully used in the preparation of radical-anion salts revealing antiferromagnetic exchange interactions in their spin systems and conductive charge-transfer complexes. 2 Although methods for the preparation of fused 1,2,5-thiadiazoles are numerous and well elaborated, there is still a lack of syntheses of derivatives containing electron-deficient heterocycles. We have found that treatment of 1,2,5-selenadiazoles fused with nitrogen heterocycles, such as piperazine and thia(selena)diazole with S 2 Cl 2 in DMF gave unexpectedly corresponding 1,2,5- thiadiazoles in high yields. This is the first case of direct substitution of the selenium to sulfur atom in 1,2,5-selenadiazoles. The driving force of this reaction is the precipitation of elemental selenium which was isolated from the reaction mixtures in practically quantitative yield. We gratefully acknowledge financial support from the Russian Foundation for Basic Research (Project ), from the Presidium of the Russian Academy of Sciences (Programme o. 8) and from the Leverhulme Trust (Project I ). 1. Todres Z.V., Chalcogenadiazoles: Chemistry and Applications, CRC Press/Taylor & Francis: Boca Raton, 2012, 290 pp. 2.. A. Semenov,. A. Pushkarevsky, E. A. Suturina, E. A. Chulanova,. V. Kuratieva, A. S. Bogomyakov, I. G. Irtegova,. V. Vasilieva, L. S. Konstantinova,. P. Gritsan,. A. Rakitin, V. I. vcharenko, S.. Konchenko, A. V. Zibarev Inorg. Chem., 2013, 52,

243 P132 ACTIVATI F HYDRPERXIDES BY TETRAALKYLAMMIUM BRMIDES E.V. Raksha 1, Yu.V. Berestneva 1,.A. Turovskij 1, M.Yu Zubritskij Donetsk ational University, Physical chemistry Department, Donetsk, Ukraine 2 - L.M. Litvinenko Institute of Physical rganic and Coal Chemistry ational Academy of Sciences of Ukraine, Donetsk, Ukraine The investigation of supramolecular catalysis of organic peroxides decomposition is the actual direction in the development of peroxide initiators chemistry. There are a wide range of catalytic systems for the radical decomposition of hydroperoxides and quaternary ammonium salts are occupied an important place among of them. The key feature of supramolecular hydroperoxides decomposition in the presence of Alk 4 Br is the complex formation between the reactants [1]. Systematic kinetic investigations of the interaction between hydroperoxides and Alk 4 Br have been carried out [1]. Activation energies of the hydroperoxides thermolysis and catalytic decomposition have shown to be change simbatically. Kinetic parameters of the hydroperoxide-catalyst complex decomposition have been determined. Lowering of the activation barrier for the complex-bonded hydroperoxide decomposition as compared with its thermolysis in acetonitrile is 40 kj mol -1. The interaction of tert-butyl as well as 1,1,3-trimethyl-3-(4-methylphenyl)butyl hydroperoxides with tetraalkylammonium bromides (Alk 4 Br) has been studied by MR spectroscopy. The complexation between reactants was observed by relative change of the chemical shifts in the MR 1 H spectra. The complex formation between the hydroperoxide molecule and corresponded quaternary ammonium salt has been proved. Thermodynamic parameters of complex formation have been determined. The equilibrium constants of complex formation (K С ) between tert-butyl hydroperoxide and Alk 4 Br have been determined both by MR 1 H and 13 C spectroscopy. The values of the Δ comp H for the hydroperoxide complex with investigated salts are negative and lie are within kj mol -1 7 in CDCl 3 solution that corresponds to the formation of weak hydrogen bonds. Similar effect has been observed in CD 3 C solution for the hydroperoxide-alk 4 Br systems. The equilibrium constant values as well as complexation enthalpies decrease with intrinsic tetraalkylammonium cation volume increasing and this effect is observed over the temperature range K. Complexation enthalpies defined by kinetic and MR spectroscopy methods coincide. The structural model has been proposed for the complex of hydroperoxides with Alk 4 Br. It includes the hydroperoxide molecule, salt cation and anion, as well as solvent molecule. Structural reorganization of the hydroperoxide fragment is the key factor of the chemical hydroperoxide activation in the presence of Alk 4 Br. [1].А. Тurovskij, E.V. Raksha, Yu.V. Berestneva, et al. in: Polymer Products and Chemical Processes. Techniques, Analysis, and Applications, Editors: R.A. Pethrick, E.M. Pearce, G.E. Zaikov. Toronto, ew Jersey: Apple Academic Press, p. P [2].А. Тurovskij, Yu.V. Berestneva, E.V. Raksha, et al. Polymers Research Journal Vol. 8, o. 2. P [3].А. Тurovskij, E.V. Raksha, Yu.V. Berestneva, M.Yu. Zubritskij. Russian Journal of General Chemistry Vol. 84, Iss P [4].А. Тurovskij, Yu.V. Berestneva, E.V. Raksha, et al. Monatshefte für Chemie - Chemical Monthly DI /s

244 P133 THE AZA-CPE-MAICH REACTI: APPLICATI T THE SYTHESIS F UATURAL L-ALAIE DERIVATIVES.K. Ratmanova, D.S. Belov, I.A. Andreev, A.V. Kurkin Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia Unnatural amino acids represent a nearly infinite array of diverse structural elements for the development of new leads in peptidic and non-peptidic compounds. Due to their seemingly unlimited structural diversity and functional versatility, they are widely used as chiral building blocks and molecular scaffolds in constructing combinatorial libraries. Herein we report the synthesis of the enantiopure unnatural L-alanine derived transoctahydrocyclohepta[b]pyrroles 5a and 5b via the aza-cope-mannich reaction (Scheme 1). Epoxide 2 (the source of chirality) was prepared according to the literature procedures from commercially available alcohol 1 applying Shi epoxidation protocol. 1 The LiCl 4 -meditated epoxide ring-opening of 2 with L-alanine ethyl ester gave the diastereomeric mixture of amino ethanols 3a and 3b. After the chromatographic separation the compounds 3a and 3b were obtained as single isomers with high enantiomeric purity (ee = 99% and 86% respectively, chiral HPLC). The hydrogenation of 3a and 3b on the Lindlar catalyst gave desired alkenes 4a and 4b and unexpected side products (S) and (R) ethyl 2 (4,5,6,7 tetrahydro 1H indol 1 yl)propanoates. Finally, carrying out the aza- Cope-Mannich reaction under previously optimized conditions 2 gave the target enantiopure products 5a and 5b without epimerization. Scheme 1. Synthesis of target compounds 5a and 5b. As a result, two diastereomeric unnatural L-alanine analogues 5a and 5b were synthesized in 5 steps from commercially available materials. The study showed that conditions of the aza-cope- Mannich reaction are mild enough to be applied in the complex settings, for example, to the synthesis of molecules with several stereocenters which are prone to racemization. 3 This study was supported by the Russian Foundation for Basic Research (RFBR), Russia (Projects o , , ). References: 1. Wang, Z.-X.; Cao, G.-A.; Shi, Y. J. rg. Chem. 1999, 64, Belov, D. S.; Lukyanenko, E. R.; Kurkin, A. V.; Yurovskaya, M. A. J. rg. Chem. 2012, 77, Ratmanova,. K.; Belov, D. C.; Andreev, I. A.; Kurkin, A. V. Tetrahedron: Asymmetry 2014, 25,

245 P134 MECHAISTIC STUDIES F PALLADIUM-MEDIATED ALKYE ISERTI REACTI USIG ELECTRSPRAY IIZATI TADEM MASS SPECTRMETRY K.S. Rodygin 1, L.L. Khemchyan 2, V.P. Ananikov Saint Petersburg State University, Institute of Chemistry, Stary Petergof, Russia 2 -. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia Rapid development of transition metal catalysis allows rational design of a new methodology to carry out three-component coupling. To achieve this aim challenging question concerning mechanistic features of insertion reaction should be resolved. [1] xidative addition of an aryl halide to Pd in Pd(PPh 3 ) 4 (a common source of Pd in cross-coupling reactions) is the first step in the catalytic cycle. Addition of an alkyne to the mixture containing Pd(PPh 3 ) 2 ArX results in the formation of another intermediate, Pd(Ar)(PPh 3 ) 2 (alkyne)x. The intermediate containing the alkyne-unit has three possibilities to evolve: π-complex, acetylide or vinyl complex (insertion product). For development of the present project it was important to reveal the nature of transition metal intermediates and their role in the catalytic cycle in order to improve selectivity and scope of three-component coupling reaction. The questions of key importance in this regard (see Scheme): how facile is the insertion reaction? And what types of complexes π-complex, acetylide or vinyl complex are formed? Few important features of the studied system deserve a note. xidative addition proceeds with formation of Pd complex, the corresponded ion was detected as [Pd(PPh 3 ) 2 Ph] +. The elimination of PPh 3 -containing species is typical and expected under these conditions. More interesting series of alkyne insertions into Pd-C bond starting from initial complex lead to the formation of Pd-containing vinyl complexes. Reductive elimination results in formation of corresponded substituted alkenes, dienes, triene and tetraene. ote, formation of these Pd-free olefinic species provides an evidence for the fact of alkyne insertion into Pd-C bonds. n the next stage ESI-(+MS/MS) experiment via collision-induced dissociation (CID) was performed. The detected fragment ions serve as an additional evidence for the investigated alkyne insertion step. In the present study we were able to distinguish π-complex and insertion intermediate using ESI-(MS/MS) experiment. K.R. gratefully acknowledges Saint Petersburg State University for a postdoctoral fellowship ( ). References [1] Hydrofunctionalization, V.P.Ananikov, M.Tanaka (Eds.), Springer, 2013, Heidelberg. ISB

246 P135 FACILE AD EFFICIET SYTHESIS 2-AMI-4H-CHRMEES VIA SLVET-FREE CASCADE ASSEMBLIG F SALICYLALDEHYDES AD CYAACETATES F.V. Ryzhkov, R.F. asybullin, M.. Elinson. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation 2-Amino-4H-chromenes (or 2-amino-4H-benzo[b]pyranes) are of particular interest as they belong to privileged medicinal scaffolds serving for generation of small-molecule ligands with highly pronounced spasmolitic-, diuretic-, anticoagulant-, and antianaphylactic activities [1]. The current interest in 2-amino-4H-chromenes bearing nitrile functionality arises from their potential application in the treatment of human inflammatory TFα-mediated diseases, such as rheumatoid and psoriatic arthritis, and in cancer therapy [2]. The development of solvent-free organic synthesis has become an important research area. This is not only due to the need for the more efficient and less labour-intense methodologies for the synthesis of organic compounds, but also because of the increasing importance of the environmental considerations in chemistry. The elimination of volatile organic solvents in organic synthesis is also the most important goal in green chemistry. We were prompted to use a convenient and facile solvent-free cascade methodology for the synthesis of 2-amino-4H-chromene scaffold from salicylaldehydes and cyanoacetates. We have found that potassium fluoride as catalyst can produce, under solvent-free mild conditions, a fast and selective cascade trasformation of salicylaldehydes and cyanoacatates into substituted at ambient temperature 2-amino-4H-chromenes chromenes in 88 98% yields. The catalytic procedure utilizes simple equipment; it is easily carried out and is valuable from the viewpoint of environmentally benign diversity-oriented large-scale processes. This efficient potassium fluoride catalyzed solvent-free approach to substituted 2-amino-4H-chromenes represents a new synthetic concept for cascade reactions, and allows for the combination of the synthetic virtues of conventional cascade processes with ecological benefits and convenience of solvent-free procedure. 1. H. Aryapour, M. Mahdavi, S.R. Mohebbi, Frch. Pharm. Res., 2012, 35, 9, J. Skommer, D. Wlodkowic, M. Matto, M.Eray, J. Pelkonen, Leukemia Res., 2006, 30,

247 P136 A EW 3D CHEMICAL FRMULAS FR AALYZIG F GEMETRICAL STRUCTURES F ACTIVE BIMLECULES I «STRUCTURE-ACTIVITY» PRBLEM E.A. Smolenskii, A.. Ryzhov, P.. Guskov, I.V. Chuvaeva.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia We suggest a new way ( the method of triangles ) to describe 3D molecule structures and solid surfaces with account their spatial geometry making the difference between stereo and conformational isomers. The new formulas allow using well-known procedures of the structure-property and structure-activity problems for large molecules. Furthermore, the method clears the novel ways of circumscribing solid surfaces and in structure-catalytic activity problems. The approach is based on taking into account every of the spatialorientated atom triples i, j, k, designating triangle. Let us to consider vertex i of the triangle and vectors V V V V V V being the entries of the i-row of the Matrix of Geometrical Distances (MGD). And ij i, j ik i k now we proceed to description in terms of the triangles matrix: 1 1 V V ij jk : V V n ; V V sin ; n ijk ijk ij jk ijk ijk ijk ij jk ijk. i j k 2 2 V V Since a vectors product determines the triangle, it automatically means an orientation of the triangle surface in space. There are 3 sets of indexes with the same direction of normal vectors n and 3 ones in opposite. ne can ijk selects internal or external triangles from the triangle matrix by following rule: triangle is external, if m i, j, k and i, j, k : n V 0 ; for triples of atoms placed on one line n is determined as vector ijk ijk m that is perpendicular to and finished on this line and started from the mass center of molecule. Changing internal triangles in the matrix by zeros, we get the external triangles matrix ijk ij jk ijk ex ijk. This matrix contains the same external triangle i, j, k three times. Thus, we define geometrical structure of a molecule. Usually a biomolecule activity is defined by small site being complimentary to its natural substrates. The site ( kcomplex ) is consisted of k inter-oriented triangles. Vector F of entry numbers a m lm for every type of the k- complex triangles in molecule with number m may be called as 3D chemical formula of this molecule. ne can selects the triangles of k-complex considering the matrix ( every type of the k-complex triangles in each compound of the set substances. Here a ( m 1, M, lm M 1 M m M 1 k C m dimension) of entry numbers a for lm P ( m (1, M ) ) of active and non-active m k l (1, C ) ) is the entry number of k-complex with number l in m - m compound, taking into account conformational isomerism, M the number of compounds, triangles in m-compound, m M 1 m m - the number of m - the general number of triangles in all substances. This matrix is based on 3D chemical formulas. Here we must using rule: any triangle being among type of triangles contained in inactive substances cannot be contained in k-complex. Remaining triangles (approximately, they are contained in k- complex; their number, as show on example of set of castanospermines tested by anti-hiv activity [G.W.J. Fleet et al. FEBS Letters V P ], as a rule, less than number of active compounds) is used for making of additive scheme for calculating of biological activity. So, 3D chemical formulas can be used for describing genes, catalyst surfaces, proteins and other biomolecules. 247

248 P137 A PRBLEM F DEFIITI F CHEMICAL EQUILIBRIUM I CTEMPRARY CHEMISTRY A.. Ryzhov, E.A. Smolenskii, P.. Guskov, M.S. Molchanova.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia Unfortunately, a many definitions of chemical equilibrium of systems exist and are used now. In process of our investigation, we find that principle of detailed equilibrium is sufficient but not necessary condition of chemical equilibrium from the viewpoint of formal kinetics. We propose a new definitions: 1. Steady-state chemical system is called chemical system with constant temperature, pressure, volume and activities of compounds. 2. Equilibrium chemical system is called steady-state and adiabatically isolated system. 3. System with detailed equilibrium is called equilibrium system with equilibrium in all elementary reactions. 4. Quasiequilibrium chemical system is open system with time of parameter stabilization been more less than time of changing of external conditions. ecessary and sufficient condition of chemical equilibrium is equality between sum of velocities of elementary reactions with getting of some compound and sum of velocities of elementary reactions with expenses of this compound for all compounds of system. For system with three compounds A B v BA v AB v CA v AC v BC C in the case of detailed equilibrium (S=[A]+[B]+[C]) A C C B B A A B B C C A k k k k k k, A Sk B A C A B A C A A B C A B A A C k k k k k k k, B Sk A B C B A B C B B A C B A B B C k k k k k k k, C Sk B C A C B C A C C B A C B C C A k k k k k k k. For this system in the common case of equilibrium 248

249 P138 SYTHESIS, STRUCTURE AD THERMAL PRPERTIES F PRPYLEE XIDE, CARB DIXIDE AD L-LACTIDE TERPLYMERS Z.. ysenko 1, E.E. Said-Galiev 1, Ya.E. Belevtsev 2, S.I. Daineko 2, M.I. Buzin 3, G.G. ikiforova 4, A.M. Sakharov D.Zelinsky Institute of rganic Chemistry of the Russian Academy of Sciences, Moscow, Russia 2 - A..esmeyanov Institute of rganoelement Compounds of Rusian Academy of Sciences, Physical Chemistry, Moscow, Russia 3 - A..esmeyanov Institute of rganoelement Compounds of Rusian Academy of Sciences, Academy of sciences, Polymer Physics, Moscow, Russia 4 - A..esmeyanov Institute of rganoelement Compounds of Rusian Academy of Sciences, Polymer Physics, Moscow, Russia Poly(propylene carbonate) (PPC) is a sustainable polymer that undergoes complete ash-free incineration accompanied by the formation of C 2 and H 2. PPC is prepared by copolymerization of propylene oxide (P) with C 2 and it exhibits attractive physical and mechanical properties responsible for its potential practical applications. It is known that ester units introduction into a polymer chain promotes increasing its biodegradability. Copolymers with different L-lactide concentrations were synthesized in the presence of zinc adipate The combination of 1 Н, 13 С, and 2D { 1 Н- 13 С}HMBC MR, DSC, FT-IR spectroscopy, and GPC study results allows one to assume that copolymerization of СО 2, P and L-lactide yields to partially crystalline terpolymers composed of propylene carbonate blocks combined with L-lactic acid blocks and may be depicted by segment II of structure represented onto Scheme. The synthesis of the terpolymers is not aggravated by side reactions. o inversion of the configuration of L-lactide occurs during its addition to the polymer chain and the copolymer possesses optic activity that depends on the L-lactide concentration in its chain. All possible types of the P addition (head-to-head, head-to-tail, and tail-to-tail), where head-to-tail addition predominates, are found in the propylene carbonate blocks. L-Lactic acid content increase was shown to be accompanied with elevation of terpolymers onset degradation temperature values. The research was supported by the Russian Ministry of Education and Science (Contract o ). 249

250 P139 SIMPLE PRECURSRS FR THE REGISELECTIVE SYTHESIS F METHYLEE-EXPADED AALGUES F C-UCLESIDES V.K. Brel 1, A.V. Samet 2, L.D. Konyushkin 2, V.V. Semenov A.. esmeyanov Institute of rganoelement Compounds 2 -. D. Zelinsky Institute of rganic Chemistry ucleosides with heterocyclic base linked to sugar through C C bond instead of C attachment in natural nucleosides attract much attention because of their chemical and enzymatic stability. Compounds with methylene group inserted between the ring oxygen and the carbon atom linked to the base moiety are considered as ring-expanded (six-membered ring) analogues of nucleosides (Figure 1, A). Several of these molecules showed potent antiviral and antitumor activity. We have developed the synthesis of C2 chiral derivatives of dihydrolevoglucosenone 1a, 2a, and 3 7 as simple precursors for preparation of methylene-expanded C-nucleosides (A), using pyrolysis of cellulose as a key step followed by hydrogenation of LG and introduction of vinyl and ethynyl fragments to 2-position. F ig u re 1 A 6 4 H 5 H e t C Cellulose H LG 1 stainless steel autoclave 2% Pd/C (Sibunit) EtAc, 40 o 20 bar, 8 h DLG 85% HC CMgBr H 2 C CMgBr THF, 40 o, 2 h Et 2, rt, 2 h R 3: Ph 4: p-me-ph 5: p-f-ph 6: Ac R 54-75% RC + - Et 2, -40 o, 3 h H H H PhCH 2 3 Cu(Ac) 2 H 2, rt, 1 h 1a CH + 63% CH 42% 2a + CH 2 CH 2 84% H H CH 2 Ph 7 1b 4.8% 3.8% 2b The opening of 1,6-anhydrohexitols acetal ring could be used for transformation of derivatives 3 7 into methylene-expanded C-nucleosides (Figure 1, A). 250

251 P140 SYTHESIS AD BILGICAL EVALUATI F FURAALLCLCHICIIDS E.S. Schegravina 1, Yu.V. Voitovich 1,.S. Sitnikov 1, V.I. Faerman 1, V.V. Fokin 1, H.-G. Schmalz 2, S. Combes 3, D. Allegro 4, P. Barbier 4, I.P. Beletskaya 5, E.V. Svirshchevskaya 6, A.Yu. Fedorov Department of rganic Chemistry, izhny ovgorod State University, Gagarina av. 23, izhny ovgorod , Russian Federation 2 - University of Cologne, Department of Chemistry, Koln, Germany 3 - Institut Paoli-Calmettes, Aix-Marseille Universite, Laboratory of Integrative Structural and Chemical Biology, Marseille, France 4 - Aix-Marseille Universit, ISERM UMR_S 911, CR2 F-13005, Marseille, France 5 - M.V.Lomonosov Moscow State University, Department of Chemistry, Moscow, Russian Federation 6 - Shemyakin-vchinnikov Institute of Bioorganic Chemistry RAS, Moscow, Russian Federation A series of conformationally flexible furan-derived allocolchicinoids was prepared from commercially available colchicine in good to excellent yields using a three-step reaction sequence 1. Compounds containing a hydroxyl group in the pseudo-benzylic position of the furan side chain exhibited high cytotoxicity toward epithelial and lymphoid cell lines (AsPC-1, HEK293 and Jurkat) in the nanomolar concentration range. In vivo studies also demonstrated significant activity of compounds bearing a hydroxymethyl fragment in the α-position of the furan ring against the tumor growth without symptoms of neurotoxicity. Acknowledgment We thank the Russian Foundation for Basic Research (projects and a), The Ministry of Education and Science of The Russian Federation (project /K). The research is partly supported by the grant 02.В of The Ministry of Education and Science of the Russian Federation to Lobachevsky State University of izhni ovgorod. References 1. Voitovich, Yu.V., Sсhegravina, E.S., Sitnikov,.S. Faerman, V.I., Fokin, V.V., Schmalz, H.-G., Comes, S., Allegro, D., Barbier, P., Beletskaya, I.P., Svirshchevskaya, E.V., Fedorov, A.Yu. Synthesis and biological evaluation of furanoallocolchicinoids. J. Med. Chem (submitted) 251

252 P141 TETRAMETHYLEECYCLCTAE A BASIS FR PLYSPIRCYCLIC SMALL RIG ARCHITECTURES K.. Sedenkova, E.B. Averina, S.G. Bakhtin, T.S. Kuznetsova,.S. Zefirov Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia 1,3,5,7-Tetrakis(methylidene)cyclooctane (1, TMC) a symmetric tetraene with highly reactive exo-cyclic double bonds represents a promising starting compound for the synthesis of polyspirocyclic small ring structures, including rotanes and heterorotanes. evertheless, up to date the synthesis of TMC was mentioned in one short communication without an experimental procedure [1]. We developed a straightforward synthesis of TMC from commercial adamantane- 1,3-dicarboxylic acid (2). The key stage of the synthesis is fragmentation of adamantane pattern of tetrabromide 3 under the treatment with zinc. CH CH 2 Br 4 steps Zn, ai, a 2 C 3 Br 74% CH DMF, 60% CH 2 Br Br (TMC) TMC was shown to demonstrate high reactivity toward diazomethane, dihalocarbenes and epoxidizing reagents, undergoing multiple cyclopropanations or epoxidations of four double bonds to yield polyspirocyclic products 4 6. X 4, X=CH 2, 80% X [1+2]-cycloaddition 5a, X=CCl 2, 95% 5b, X=CBr 2, 65% or epoxydation 5c, X=CBrF, 50% X X 6, X=, 50% 1 Stereochemical features of polyspirocyclopropanated compounds 5,6 have been thoroughly examined in experimental (MR) and theoretical (DFT) studies. Comprehensive stereochemical assignment of TMC adducts with dihalocarbenes and polyspiroepoxy products was achieved. In course of the work we have found that carrying out the fragmentation of adamantane derivative 3 in presence of traces of water leads to the formation of bis(methylidene)bicyclononane 7. The addition of dihalocarbenes to diene 7 was shown to be stereoselective, giving solely the products of exo-addition to double bonds 8a c, that was by unambiguously proved by RSA for 8a. 3 Zn, ai, a 2 C 3 DMF/H 2, 160 o C, 25% 7 CXY CHX 2 Y, ah aq 8a, X=Y=Cl, 87% 8b, X=Y=Br, 72% CH 3 TEBA, CH 2 Cl 2 CH 8c, X=Br, Y=F, 43% 3 In conclusion, we elaborated a preparative gram-scale approach to TMC and obtained a series of unique polyspirocyclic structures starting from this highly reactive tetraene. We thank the Russian Foundation for Basic Research (Projects mol_а, a) and Presidium RAS (program 8P) for financial support of this work. [1] Stepanov, F..; Sukhoverkhov, V. D.; Baklan, V. F.; Yurchenko, A. G. Zh. rg. Khim. 1970, 6, ; J. rg. Chem. USSR (Engl. Transl.) 1970, 6, CXY 252

253 P142 USIG HAuCl 4 AS A SIGLE SURCE F METAL T PRDUCE SLUBLE Au(Pr 3 )Cl CMPLEXES AD Au(0) PARTICLES A.E. Sedykh 1, S.S. Zalesskiy 2, A.S. Kashin 2, V.P. Ananikov Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia; Higher Chemical College, Russian Academy of Sciences, Moscow, Russia 2 - Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia A simple approach was developed for the synthesis of homogeneous and heterogeneous gold catalysts. ne of the most common gold compounds HAuCl 4 was used as a single source of metal. Efficient one-pot synthesis procedure was created for preparation of gold complexes with various phosphine or phosphite ligands Au(PR 3 )Cl (90 99% yield). The developed method gives excellent results even for electron-deficient ligands and sterically hindered Buchwald-type phosphines. Various gold(0) nanoparticles were prepared using simple and available reductants. The morphology of metal particles was studied and characterized with high-resolution field-emission scanning electron microscopy (FE-SEM). It was found that the size and shape of the growing particles can be controlled simply by selecting a reducing agent. Several unique types of structured gold materials were prepared, such as particles arranged in a well-developed porous network, hierarchical agglomerates and metal mirror composed of ultrafine particles.[1]. [1] Zalesskiy, S.S.; Sedykh, A.E.; Kashin, A.S.; Ananikov, V.P J. Am. Chem. Soc. 2013, 135,

254 P143 MLECULAR ITERACTIS AD EXTRACTI F PEPTIDES I IIC LIQUIDS SYSTEMS M.M. Seitkalieva, V.V. Kachala, K.S. Egorova, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia In past decade, ionic liquids (ILs) have been weightiest matter because of their well-favored properties for variety of physical, chemical and biological application. [1] The technologies of ILs mediated extraction have shown the good prospects for replacing traditional methods in separating natural bioactive homologues. They widely have been investigated as extracting phases in liquid-liquid and aqueous two-phase systems for amino acids and proteins. For peptides no such large achievement were reached and the mechanisms of peptide IL interactions remain to be established. Recently, we have studied interactions of imidazolium-based ILs with peptides built from L-alanine and L-valine by MR spectroscopy. [2] High sensitivity of ILs to the nature of peptides and remarkably capability to distinguish a small change in the amino acid sequence was demonstrated, that allowed further to study the molecular nature of the separation process. Hereinafter the back extraction of peptides in a two-phase ionic liquid organic solvent system was performed and mechanism of peptide transition was studied. The slice-selective MR experiments were applying for effectively monitoring extraction process that allowed discovering the molecular mechanism of peptide transition from the ionic liquid to organic phase. The results suggested that the extraction occurred by molecular diffusion of individual peptide molecules, which passed from IL to the organic solvent without structural changes. The selection of the extraction system was carried out, and imidazolium-based ILs: ethyl acetate - petroleum ether system was used for effective partition of structurally similar peptides. Was demonstrated that the extraction efficiency and selectivity increased with increasing the molecular concentration of peptides. btained results have potential application in separation and analysis of biomolecules. [1] (a) V. P. Ananikov, Chem. Rev., 2011, 111, 418; (b) K. S. Egorova and V. P. Ananikov, ChemSusChem, 2014, 7, 336. [2] M. M. Seitkalieva, A. A. Grachev, K. S. Egorova and V. P. Ananikov, Tetrahedron, 2014, /j.tet s. 254

255 P144 SYTHESIS AD BILGICAL EVALUATI F AALGS F ATURAL ATIMITTIC PRDUCTS USIG PARSLEY AD DILL SEED EXTRACTS D.V. Tsyganov 1,.B. Chernysheva 1, D.V. Demchuk 1, A.V. Samet 1, L.D. Konyushkin 1, M.. Semenova 2, V.V. Semenov D. Zelinsky Institute of rganic Chemistry 2 -. K. Kol tsov Institute of Developmental Biology Analogs of antimitotic natural products podophyllotoxin (PT) and combretastatin A-4 (CA4) as well as plant-derived glaziovianin A were synthesized using allylpolyalkoxybenzenes from dill and parsley seed oil. The targeted molecules were evaluated in vivo in a phenotypic sea urchin embryo assay for antimitotic and microtubule destabilizing activity. Structure activity relationship studies identified CA4 analogs with 3,4,5-trimethoxyphenyl and 3,4-methylenedioxy-5-methoxyphenyl ring A and 4-methoxyphenyl ring B as potent antiproliferative agents with high cytotoxicity against a panel of 60 human cancer cell lines including multi-drug resistant cells. The most active aza- and oxa-pts featured myristicin-derived ring E. Cytotoxic effect of tested compounds was attributed to microtubule destabilization resulted in cell cycle arrest followed by apoptotic cell death. The effective threshold concentrations (EC) resulting in mitotic abnormalities in the sea urchin embryos are presented in Figure. Considering these encouraging data from phenotypic and mechanistic studies, some compounds may prove to be lead candidates for further in vivo studies to assess its potential as an anti-tumor agents. 255

256 P145 STRUCTURES F CAPSULAR PLYSACCHARIDES F SCMIAL PATHGE ACIETBACTER BAUMAII AD THEIR CLEAVAGE BY SPECIFIC BACTERIPHAGE TAIL-SPIKE DEPLYMERASES A.S. Shashkov 1, S.. Senchenkova 1, Y.A. Knirel 1, M.M. Shneider 2, K.A. Miroshnikov 2, A.V. Popova 3,.V. Volozhantsev D.Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - M.M. Shemyakin & Y.A. vchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, Moscow, Russia 3 - State Research Center for Applied Microbiology and Biotechnology, bolensk, Moscow Region, Russia osocomial infections due to multidrug-resistant pathogen Acinetobacter baumannii have become increasingly common. Phage therapy is promising for their treatment. A prerequisite of bacteriophage adsorption on the bacterial cell surface necessary for the infection and the following lysis of the cell is the cleavage of the protecting bacterial capsular polysaccharide (CPS) by a specific structural depolymerase (phage tail spike). To develop the biochemical basis for phage therapy of A. baumannii infections we studied structures of the CPSs of these bacteria and mechanisms of the CPS depolymerisation by bacteriophage tail spikes. CPS structures of 5 strains of A. baumannii (28, 1053, 1432, 5075 and ACICU) were established using chemical methods along with 1 H и 13 С MR spectroscopy. Degradation of the CPSs from A. baumannii 28 and 1053 was performed with recombinant tail-spike depolymerases of bacteriophages Fri1 and AP22, respectively. Structures of the CPSs and degradation products were established by 1 H and 13 C MR spectroscopy and high-resolution ESI MS. FriI glycosidase hydrolysed the CPS of strain 28 at one of the glycosidic linkage to give mainly a nonasaccharide composed of three CPS repeats (Scheme 1). AP22 lyase cleaved the CPS of strain 1053 by -elimination in a hexuronic acid residue to give unsaturated trisaccharide (major) and hexasaccharide (minor) (Scheme 2). Scheme 1. Depolymerisation of CPS of A. baumannii 28 by phage FriI tail-spike hydrolase. QuiAc4Ac, 2,4-diacetamido-2,4,6-trideoxy-D-glucose; n = 1 (major), 0, 2-4 (all minor). Scheme 2. Depolymerisation of CPS of A. baumannii 1053 by phage AP22 tail-spike lyase. 4,5HexAcA, 2-acetamido-2,4-dideoxy-L-erythro-hex-4-еnuronic acid. 256

257 In te n s ity/a.u In te n s ity/a.u P146 PHTLUMIESCECE PRPERTIES F IDIUM-EXCHAGED ZSM-5 ZELITE A.I. Serykh Zelinsky Institute of rganic Chemistry of the Russian Academy of Sciences ptical properties of indium-exchanged ZSM-5 zeolite with different indium content have been studied. It has been found for the first time that reduced In-ZSM-5, containing low-valence In + cations exhibits strong photoluminescence emission both in UV and visible light region. The intensity of visibly light luminescence strongly increases with increase of indium content in In- ZSM-5. The emission spectrum of low-indium loaded In-ZSM-5 is represented mainly by an intense UV band at 350 nm (Fig.1). The excitation spectrum consists of three irregularly-shaped bands at about nm, 260 nm and 308 nm. Lifetime measurements show that the UV emission of this sample has a single component (approximately ms). The emission spectrum of In-ZSM-5 with high indium content (Fig. 2) is represented by two intense emission bands both in UV and visible-light regions. The visible light emission decay is complex and has a fast (10-3 ms or faster) and at least two slow components (0.05 ms and 0.2 ms). The excitation spectra of both UV and visible-light emission bands are represented by three irregular shaped peaks at nm, 260 nm and nm. These peaks can be induced by the electronic excitations transitions similar to those X 1 Σ + (0 + ) C 1 (1), X 1 Σ + (0 + ) B 3 1(1) and X 1 Σ + (0 + ) A 3 0(0 + ) in indium halides or 1 S 0 1 P 1, 1 S 0 3 P 2 and 1 S 0 3 P 1 transitions in indium-doped alkali halides (C, B and A transitions). The emission in In-ZSM-5 occur due to irradiative transition from the lowest excited state (which is a triplet state according to its lifetime) The UV luminescence most probably is associated with isolated In + cations, while the visible-light emission can be related to the formation of In + oligomers or clusters in the excited state. E xc ita tio n Em ission 350 Fig.1. Emission and excitation spectra of lowindium-loaded In-ZSM-5 (4 wt.% In) reduced in hydrogen at 823 K and evacuated at the same temperature for 2 h W a v e le n g th /n m E x c ita tio n a E m is s io m Fig. 2. Emission and excitation spectra of highindium-loaded In-ZSM-5(9 wt. % In) reduced in hydrogen at 823 K and evacuated at the same temperature for 2 h. b c W a v e le n g th /n m 257

258 P147 CATALYTIC XIDATI F LEFIS BY TBHP I THE PRESECE F TRASITI METALS M.Y. Sharipov, A.. Terent ev. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences Moscow, Leninsky prospekt, 47, Russia The transition metal catalyzed selective oxidation of organic compounds with the aim of organic peroxides preparation is a demanded field of the oxidative processes chemistry. The publications of recent years show that organic peroxides possess a high antimicrobial, antiparasitical and fungicidal activity. It was discovered that cyclic diperoxides reveal a high antischistosomal activity (IC 50 <15μM) [1]. The role of t-bu and t-bu radicals in oxidative reactions of alkanes, alkenes and alkylbenzenes with t-buh was earlier showed by Minishi group; the processes were catalyzed by Fe(III) or Mn(III) porphyrins [2]. In this study the reaction conditions were found under which a selective oxidation of olefins by tertbutyl hydroperoxide gives vicinal bis-peroxides in the presence of transition metal complexes. Proposed mechanism involves the stages of oxidation of metal complex by tert-butyl hydroperoxide (a). Radical t-bu reacts with t-buh in nonbasic solvent giving t-buо radical (b), which adds to substrate giving the corresponding radical (с); this latter one is then oxidized via a ligandtransfer process (d). Mn(III) salts transfer a peroxy-group to the carbon-centered radical, while Mn(II) salts decompose t-buh giving t-bu (e). This work is supported by the Grant of the Russian Foundation for Basic Research (Grant a) and the Grant of the Program of Supporting for Basic Research of the Presidium RAS. 1. K. Ingram, I.A. Yaremenko, I. Krylov, L. Hofer, A..Terent'ev, J.Keiser. J. Med. Chem., 2012, 55 (20), c F. Minisci, F. Fontana, S. Araneo, F. Recupero, S. Banfi and S. Quici. J. Am. Chem. Soc., 1995, 117 (1), c

259 P148 E-PT TW-STEP SYTHESIS F PTICALLY ACTIVE 1-AMI PHSPHATES BY PALLADIUM-CATALYZED HYDRGEATI/HYDRGELYSIS F 1-(2-PHEYLHYDRAZ) PHSPHATES I.A. Shergold,.S. Goulioukina, I.P. Beletskaya Lomonosov Moscow State University, Chemistry Department, Moscow, Russia Heterogeneous palladium catalysts such as Pd/C or Lindlar catalyst are routine and the most popular hydrogenation tool. ver the recent decade chiral palladium complexes of diphosphine ligands have emerged as new efficient metal catalysts for homogeneous asymmetric reduction of C=C, C=, and especially C=C or C= double bonds within a wide variety of prochiral substrates. [1] Thus we have successfully employed this methodology for the preparation of nonracemic 1-hydroxy [2] and -hydroxy-1-amino phosphonates [3] starting from carbon-heteroatom unsaturated precursors. Herein we present our preliminary results on the synthesis of optically active 1-amino phosphonates (a well-known class of bioactive compounds [4] ) by two-step procedure taking advantages of both homogeneous and heterogeneous palladium catalysts. In search of easy-to-use starting substrates we opted for 1-(2-phenylhydrazono) phosphonates 1 which were isolated as the single (Z)-isomers, the double bond geometry having been confirmed by X-ray crystallographic analysis. We have shown that phosphonates 1 can be smoothly reduced by hydrogen gas with Pd(Ac) 2 /(R)-Cl-Me-BIPHEP as the catalyst and (1S)-(+)-10-camphorsulfonic acid (CSA) as the activator to furnish corresponding 1-(2-phenylhydrazino) phosphonates 2 in high yields and enantiomeric excess 90 94%. The subsequent hydrogenolysis of intermediate products 2 was performed in situ over 10% Pd/C without any loss of optical purity. References: 1 a) Q.-A. Chen, Zh.-Sh. Ye, Y. Duan, Y.-G. Zhou. Chem. Soc. Rev. 2013, 42, ; b) J.- H. Xie, Sh.-F. Zhu, Q.-L. Zhou. Chem. Rev. 2011, 111, S. Goulioukina, G.. Bondarenko, A.V. Bogdanov, K.. Gavrilov, I.P. Beletskaya. Eur. J. rg. Chem. 2009, S. Goulioukina, I.A. Shergold, G.. Bondarenko, M.M. Ilyin, V.A. Davankov, I.P. Beletskaya. Adv. Synth. Catal. 2012, 354, a) F. rsini, G. Sello, M. Sisti. Curr. Med. Chem. 2010, 17, ; b) P. Kafarski, B. Lejczak. Posphorus, Sulfur, and Silicon 1991, 63,

260 P149 CARBHYDRATE-BASED PHSPHIES AD THEIR SUPPRTED PALLADIUM CMPLEXES: APPLICATI I SUZUKI-MIYAURA AD HECK REACTIS J. Shi 1, Zh. Zhou 2, H. Zheng 1, Q. Zhang College of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming , China 2 - College of Chemistry and Chemical Engineering, Gannan ormal University, Ganzhou, , China Several carbohydrate-based phosphines derived from glucose, (methyl 3-deoxy-4,6-phenylmethenyl-α-D-altropyranosido-3-)disubstituted-phosphine, and some of their palladium complexes have been synthesized and fully characterized. The well defined palladium complexes and those generated in situ are highly effective for Suzuki-Miyaura and Heck reactions. The oxygen atoms in the carbohydrate unit were found to participate in catalytic cycle and contribute to catalytic activity. Ph Ph R 2 P Pd 2 Me 2 Me Cl Pd Me 2 2) ame 2 Ph R 2 P 1 H R = Ph, Cy, Bu t 1) Pd(CD)Cl Me 2 2) ame This project was supported by the ational atural Science Foundation of China (o ), the atural Science Foundation of Fujian Province (2011J01033). References: 1. Shi, J.-C.; Zhou, Z.; Zheng, S.; Zhang, Q.; Jia, L.; Lin, J. Tetrahedron Lett. 2014, 55, Zheng, S.; Jia, L.; Liu, Z.; Jiang, D. Huang, Y.; ong, L.; Zhang, Q.; Shi, J.-C. Chin. J. rg. Chem. 2014, 34, DI: /cjoc Shi, J.-C.; Kang, B.-S.; Mak, T. C. W. J. Chem. Soc., Dalton Trans. 1997, Ph R 2 P R 2 P Pd 3 Me Me 260

261 P150 A EW SYTHETIC APPRACH T 3-PHSPHRYLATED PYRAZLES E.D. Shinkarev,.. Makukhin,.S. Goulioukina, I.P. Beletskaya Moscow State University, Department of Chemistry, Moscow, Russia Phosphorylated pyrazoles [1] represent intriguing structural motives for the design of biologically and pharmaceutically active compounds and are a subject of growing interest in different fields such as agrochemical and medicinal chemistry. Besides the biological properties, pyrazolyl phosphonates received considerable attention as efficient coordinating ligands and as precursors to -heterocyclic carbenes (HC). In spite of great potentialities for the practical usage, synthetic approaches to phosphorylated pyrazoles are few in number and often involve multistep reaction sequences. So the search of novel efficient methods for pyrazolyl phosphonates preparation remains an actual task. Recently we have shown that 1,3-dipolar cycloaddition reaction of aryldiazomethanes with dimethyl 1-formamidovinylphosphonate (1) affords 5-substituted dimethyl 3-formamido-4,5- dihydro-3h-pyrazol-3-ylphosphonates (2) or thermodynamically more stable isomeric 3-substituted dimethyl 5-formamido-4,5-dihydro-1H-pyrazol-5-ylphosphonates (3). The subsequent aromatization of 2 or 3 with formamide elimination and formation of 3-phosphorylated pyrazoles 4 have been performed under acidic conditions. [2] In continuation of this work, we have elaborated a simple one-pot procedure for the direct preparation of ring substituted phosphonates 4. It was found that the cycloaddition of aryldiazomethanes onto phosphonate 1 smoothly proceeds in methanol or ethanol in the presence of catalytic amounts of K 2 C 3 at room temperature to furnish 3-phosphorylated pyrazoles 4 in good to excellent yields. The methodology is compatible with various functional groups and provides a broad scope of ring substituted (5-aryl-1H-pyrazol-3-yl)phosphonates. The structure features of the products obtained will be also discussed. [1] T. E. Ali, S. M. Abdel-Kariem, Heterocycles, 2012, 85, [2]. S. Goulioukina,.. Makukhin, I. P. Beletskaya, Tetrahedron, 2011, 67,

262 P151 SYTHESIS F CHIRAL ISCYAIDES BASED β-ami ACIDS FR MULTICMPET REACTIS.I. Shmatova, D.P. Zarezin, V.G. enajdenko Department of Chemistry, Moscow State University, Leninskie Gory, Moscow , Russia It is known that peptides possess a high biological activity and could affect on different physiological processes (regulation of hormonal activity, digestion, appetite, pain, higher nervous activity, arterial pressure etc.). But the biggest drawback of peptide as therapeutic drug is its low metabolic stability. Various structural modifications of α-amino acids are using to improve stability of biological active peptides. ne of the possible modifications of α-amino acid is its homologization and replacement for β-amino acid in peptide chain. n the other hand, isonitriles is actively used in Ugi and Passerini multicomponent reaction for preparing peptides and depsipeptides. We decided to develop synthesis of new chiral isonitriles based on β-amino acids and investigated its use in multicomponent reaction for obtaining peptidomimetics containing fragment of β-amino acid. Isonitriles 4 were synthesized from commercial available -formyl-α-amino acids 1 by Arndt- Eistert reaction (preparing diazaketone 2 and subsequent Wolf rearrangement in the presence of nucleophile alcohols, amines or amino acids). Then isonitriles 4 were synthesized from obtained derivatives 3 by treatment PCl 3 /Et 3. HC R 1) ClCEt 2 R PhCAg R PCl 3 R 1 HCH 2) CH 2 2 uh Et HCH u HCH 3, u C CH 2 Cl 2 R = Ph, Me, Bn, ibu, ipr, secbu, CH 2 Indolyl; uh = R'H, R''R'''H, MeC. R'''' H 2 ew chiral isonitriles 4 participate in the Ugi reaction to give the corresponding di-, tri- or even tetrapeptide 5 in good yields. Moreover these isonitriles 4 react smoothly with carboxylic acids and ketones/aldehydes affording depsipeptides 6. R R 2 H 2 R + H 4 u C R 1 R 3 R 4 CH R 3 5 R 4 u R R 3 R 4 R + H 4 u C R 1 CH R 3 u 6 R 1 R 1 R 4 R 2 262

263 P152 MULTICMPET REACTI F 3-HYDRXYCHRME WITH ALDEHYDES AD THE MELDRUM`S ACID S.V. Shorunov, B.V. Lichitsky, A.. sipov, A.. Komogorttsev, A.A. Dudinov, M.M. Krayushkin.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 3-Hydroxychromones possess considerable interest due to their unique optical properties 1-2. Thus the chemical synthesis of the derivatives of 3-hydroxychromone is of prime interest. The convenient method of the synthesis of those compounds is the multicomponent reaction (MCR) which allows one to synthesize the broad set of the derivatives of the 3-hydroxychromones in one stage. In the present work we explored the multicomponent condensation of 3-hydroxychromone (1) with aldehydes (2) and the Meldrum`s acid (3). The condensation was carried out by refluxing the methanolic solution of the reactants for 2 hours with triethylamine employed as the base. It was demonstrated that the main products of such a reaction are esters (4). We assume that the condensation proceeds via the initial formation of the arylmethylene derivatives of the Meldrum`s acid with subsequent addition of the 3-hydroxychromone which leads to the unstable cyclic intermediates (5). Probably after formation the lactones (5) undergo the ring opening by action of methanol and triethylamine forming the final products (4). Thus we elaborated a convenient general approach to chromone esters (4) based on the multicomponent condensation of 3-hydroxychromone (1) with aldehydes (2) and Meldrum`s acid (3). References: 1. Chevalier K, Grun A, Stamm A, Schmitt Y, Gerhards M, Diller R. J. Phys. Chem., 2013, 117, Das R, Duportail G, Ghose A, Richert L, Klymchenko A, Chakraborty S, Yesilevskyy S, Mely Y.Phys.Chem.Chem.Phys, 2014, 16,

264 P153 VEL CHIRAL FLURIE-BASED PRBES FR MITRIG F ASYMMETRIC REACTIS BY MR SPECTRSCPY S.A. Shyshkanov,.V. rlov, V.P. Ananikov.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation Development of chiral molecular sensors for analysis of chiral compounds has got great attention during past decade [1]. Their main advantage over traditional chiral auxiliary reagents are both short sample preparation and analysis time allowing quick analysis of huge amounts of samples. To date enantioselective fluorescent sensors are widely used for analysis of chirality, however, MR sensors can be equally efficient to meet these needs. In the present study we have investigated the efficiency of 19 F MR spectroscopy, which combines high sensitivity and wide MR scale range of fluorine nucleus, for the quantitative analysis of chiral carboxylic acids. For this purpose fluorine-based chiral probes were synthesized starting from cheap and available R-2-amino-1-butanol (scheme 1). Scheme 1. The derivatization protocol developed during previous investigations [2, 3] was found to be efficient for analysis of carboxylic acids, containing a stereocenter in α-or β-position, directly in MR tube without isolation and purification of the resulting diastereomers (scheme 2). Scheme 2. The obtained results demonstrated the efficiency of 19 F MR spectroscopy for quick and accurate analysis of chiral carboxylic acids. The best results were obtained using a derivative containing 2- fluoro-substituted phenyl ring, which is apparently due to the ultimate contribution of the steric and electronic effects. The design criteria of the chiral probes, scope and limitations of the protocol and implementation to MR monitoring of enantiomeric excess of asymmetric reactions will be covered in the poster. Acknowledgements The research was supported by the Russian Foundation for Basic Research (project ). References 1. L. Pu, Acc. Chem. Res. 2012, 45, V. rlov, V. P. Ananikov, Chem. Commun. 2010, 46, V. rlov, V. P. Ananikov, Green Chem. 2011, 13,

265 P154 SYTHESIS F PYRIDIE FRM ALDEHYDE, ALKYE AD AMMIUM ACETATE THRUGH RHDIUM(III) CATALYZED - AULATI REACTI Y.-K. Sim, C.-H. Jun Yonsei University, Department of Chemistry, Seoul, Korea Transition metal catalyzed C-H bond activation is one of powerful tools to generate valuable carbon-carbon bond in organic synthesis. Especially, Rh(III) catalyzed heterocyclic -annulation has attracted great attention due to its numerous important applications and facile preparation of isoquinoline derivatives. 1 Despite of development of many synthetic methods for isoquinoline synthesis, only a few pyridine synthetic method have been reported. In the course of our studies on Rh(I) catalyzed hydroacylation, 2 we found a new synthetic method for pyridine synthesis which employs Rh(I) hydroacylation and subsequent Rh(III) catalyzed pyridine synthesis from the resulting, -unsaturated ketone, ammonia, alkyne and Cu(II) as oxidizing reagent. This new protocol allows to prepare multifunctional pyridine derivatives Song, G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, Jun, C.-H.; Lee, H.; Hong, J.-B.; Kwon, B.-I. Angew. Chem., Int. Ed., 2002, 41, Sim, Y.-K.; Lee, H.; Park, J.-W.; Kim, D.-S.; Jun, C.-H. Chem. Commun., 2012, 48,

266 P155 AMIIMIPHSPHRAATE AREE RUTHEIUM CMPLEXES: SYTHESIS, STRUCTURE AD СATALYSIS Y.S. Sinopalnikova, T.A. Peganova,.V. Belkova, A.M. Kalsin A..esmeyanov Institute of rganoelement Compounds of Russian Academy of Sciences, Moscow, Russian Federation Aminoiminophosphoranate (P) ruthenium complexes are scarcely explored organometallic compounds. ew 18ē (1) and 16ē (2) arene ruthenium complexes with various - and P- substituents at the P ligands were synthesized by reaction of the sodium aminoiminophosphoranates with dimeric arene ruthenium chlorides. The zwitter-ionic P ligand [1] is a strong σ, -donor, it can efficiently stabilize coordinatively unsaturated 16ē P complexes and render them as stable as their 18ē precursors. The neutral 18ē complexes 1 reversibly dissociate in solution to give cationic 16ē complexes 2, in polar solvents the equilibrium is strongly shifted to the right side. The activation barriers ( G ) for the dissociation process were estimated by EXSY and VT MR; the equilibrium parameters ( G, H, S) were found by UV-vis measurements in a wide range of temperatures ( K). The formally electron deficient 16ē complexes 2 can interact with 2ē donor ligands (MeC, Py, C) to produce 18ē cationic complexes 3, although the acetonitrile and pyridine adducts are stable only at low temperatures. These reactions were studied by MR and UV spectroscopy in a wide range of temperatures ( K) to find their thermodynamic parameters. The cationic Ccomplex is stable at ambient conditions due to the strong -acceptor ability of this ligand. It was fully characterized by MR and the structure was determined by X-ray analysis. The complexes 1 and 2 were tested in model catalytic transfer hydrogenation of acetophenone in isopropanol. Interestingly, the 18ē complexes are an order of magnitude more active than their 16ē counterparts having non-coordinating anions (PF 6 -, BF 4 -, BAr F 4 - ). The activity is strongly enhanced when more electron-releasing groups (alkyls) at - and P- are used. The tentative mechanism is proposed. The authors thank the Russian foundation for basic research (grant RFBR ) for financial support. [1] Peganova, T.A.; Valyaeva, A.V.; Kalsin, A.M.; Petrovskii, P.V.; Borissova, A..; Lyssenko, K.A.; Ustynyuk,.A. rganometallics 2009, 28,

267 P156 CMPARIS F PARTICLE SIZE EFFECT I CH 4 XIDATI VER Pt VS Pd CATALYSTS A.M. Batkin 1,.S. Teleguina 1, G.. Bragina 1, A.K. Khudorozhkov 2, V.I. Bukhtiyarov 2, A.Yu. Stakheev Zelinsky Institiute of rganic Chemistry, Catalysis division, Moscow, Russia 2 - Boreskov Institute of Catalysis, SB RAS, ovosibirsk, Russia Catalytic combustion of methane is a promising automotive exhaust gas after-treatment technology. Supported noble metals (e.g. Pt and Pd) have been reported as active catalysts for methane oxidation reaction and are preferentially used in automotive converters in spite of their high cost. ne of the most important factors influencing the efficiency of noble metal catalyst is the size of metal particles. High metal dispersion increases the fraction of atoms accessible for a reaction. n the other hand, turnover rates of oxidation reactions may depend significantly on the size of metal particles (particle size effect). As a result, overall activity of the catalyst becomes a function of metal dispersion (fraction of exposed atoms) and the particle size effect, and careful management of metal particle size is required for achieving optimal performance and/or minimization of noble metal loading. In the present study we compared particle size effect in CH 4 oxidation process over Pt/Al 2 3 and Pd/Al 2 3. Catalytic tests were complemented by in-situ XPS study of the oxidation state of Pt and Pd particles under reaction conditions for revealing a nature of the observed catalytic effects. Catalytic studies demonstrated different dependencies of TF on metal particle size for Pd and Pt catalysts. Particle size effect for Pd catalysts is significantly pronounced: TF increases by more than order of magnitude with increase in d Pd from 1 to 22 nm. Therefore, the most favorable performance is observed for the catalyst with Pt particle size ~ 4 nm. For Pt catalysts TF increases only by ~ 2-3 times with increasing particle size from 1 to 3-4 nm, and remains essentially constant when d Pt exceeds 4 nm. As a result, the sample with maximal Pt dispersion (d Pt = 1.2 nm) demonstrates the best overall activity in CH 4 oxidation among Pt catalysts. Results of in-situ XPS studies indicate that Pd particles remain in oxidized state in the course of the reaction within the whole range of particle sizes (1 22 nm). n the other hand, for Pt catalysts with bigger metal particles, XPS data showed that Pt remains mainly in the metallic state. These data suggest that the observed dependence of the catalytic activity on metal particle size may be associated with the change of the reaction pathway from Mars van Krevelen mechanism for Pd catalysts to Langmuir Hinshelwood kinetics for Pt samples. Acknowledgement: Financial support by RFBR grant # a is gratefully acknowledged 267

268 P157 SELECTIVITY CTRL I SEMIHYDRGEATI F SUBSTITUTED ALKYES BY Pd PARTICLE SIZE Selectivity in alkene P.V. Markov 1,.V. Turova 1, I.S. Mashkovsky 1, A.K. Khudorozhkov 2, V.I. Bukhtiyarov 2, A.Yu. Stakheev Zelinsky Institiute of rganic Chemistry, Catalysis division, Moscow, Russia 2 - Boreskov Institute of Catalysis, SB RAS, ovosibirsk, Russia Alkynes are versatile reagents in organic synthesis since C C group can be easily transformed to a cis-alkene through stereoselective addition of hydrogen molecule. This so-called semihydrogenation is often an important step in industrial processes as well as in laboratory-scale reactions. However, careful control of stereoselectivity and minimization of over-hydrogenation is required. In this work we studied a relationship between the size of Pd nanoparticles (ranging from 1.5 to 22 nm) in 1%Pd/Al 2 3 catalyst and the activity/selectivity in liquid-phase diphenylacetylene (DPA) hydrogenation. The data obtained reveal a significant increase in turnover frequency (calculated per surface Pd atom) and pronounced improvement of the in the catalyst selectivity with the increase in Pd particle size (Fig. 1, (a) and (b) respectively). The observed relationship can be explained by a strong adsorption of bulky alkyne and alkene molecules on low-coordinated surface atoms of small Pd nanoparticles. Strong absorption reduces TF due to competition between adsorbed DPA molecules and hydrogen. Moreover, strong adsorption of the intermediate alkenes impedes their desorption and favors secondary stage of hydrogenation. n the other hand, when Pd particles grow in size, the percentage of lowcoordinated palladium surface atoms rapidly decreases. This improves turnover frequency and enhances selectivity of the process. TF, s Pd particle size, nm (a) 96% 94% 92% 90% 88% 86% 84% Pd particle size, nm Fig. 1. Effect of Pd particle size on TF [n(dpa)/n(pd surf )*s -1 ] (a) and selectivity toward stilbene formation (b) in the course of DPA hydrogenation over 1%Pd/Al 2 3. Acknowledgement: Financial support by RFBR grant # is gratefully acknowledged (b) 268

269 P158 VEL CATALYST FR SELECTIVE HYDRGEATI F ACETYLEIC BD BASED PD APARTICLES ECAPSULATED I METAL-RGAIC FRAMEWRK (H 2 )-MIL-53(AL) V.I. Isaeva, P.V. Markov,.V. Turova, I.S. Mashkovsky, G.K. Kapustin, L.M. Kustov, A.Yu. Stakheev Zelinsky Institiute of rganic Chemistry, Catalysis division, Moscow, Russia Selective semihydrogenation of an acetylenic function is a demanding task. ot only does the stereoselectivity (E/Z ratio) need to be controlled, but the hydrogenation of the resulting olefin to alkane must be suppressed as well. During the last decade the metal-organic framewoks (MFs) received a considerable attention as metal carriers for heterogeneous catalysis, which enable fine tuning both activity and selectivity of the resulted heterogeneous systems. In this study we explored catalytic performance the novel catalyst on the basis of Pd nanoparticles encapsulated in microporous metal-organic frameworks MIL-53(Al) and H 2 -MIL-53(Al) in liquid-phase hydrogenation of diphenylacetylene (DPA) as the model substrate: P h P h H 2 H 2 P h P h (c is ) P h P h (tra n s ) P h P h The important task of this research was the elucidation of an impact of the metal-organic framework texture and the functional groups (H 2 -) in organic linker on the catalytic performance of enacapsulated Pd Ps composites. Main results The catalysts demonstrate high activity and excellent selectivity in DPA semihydrogentaion (Table 1). Selectivity toward alkene (diphenylethene - DPE) formation exceeds 90% at dipehylacetylene conversion as high as 95%. The catalysts also show high stereoselectivity (E/Z ratio) toward formation of cis-isomer ( > 97%) and favorable stability. Table 1. Ts and selectivity parameters in DPA hydrogenation P H2 = 5 bar, T react = 25 o C, [DPA]/Pd ~ 4000 Catalyst Solvent ТО DFA, s -1 ТО DFE, s -1 r DFA /r DFE S DFE * S cis/(cis+trans) * 1%Pd/MIL-53(Al) %Pd/H 2 -MIL- n-c 6 H (Al) 1%Pd/MIL-53(Al) % 97.8% 1%Pd/H 2 -MIL- 53(Al) CH 3 H % 98.3% * selectivity to alkene and cis-isomer was measured DPA conversion ~ 95% The data obtained imply that Pd/MIL-53(Al) nanocomposites can be considered as a promising candidate for development of highly effective catalysts for liquid-phase selective bond hydrogenation of C C bond. Acknowledgement: Financial support by RFBR grant # is gratefully acknowledged 269

270 P159 KIETIC RESLUTI F RACEMIC GERAYLCYCLHEXYLACETIC ACID T EATIMERS S.G. Zlotin, G.V. Kryshtal, G.M. Zhdankina, A.A. Sukhanova, A.S. Kucherenko, B.B. Smirnov, V.A. Tartakovsky.D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Leninsky prospekt, 47, Moscow, Russia Geranylcyclohexylacetic acid 1 is the active substance of Cygerole that had manufactured in Russia and used for curing of wounds, in particular surgery wounds, radiation or trophic ulcers and burns. Furthermore, isoprenoid acids turned to be promising as tracking drugs for cell therapy of various human diseases and injuries of vital organs and tissues with mesenchymal stem cell (MSC) and MSC-derived cardiomyoblasts [1]. Acid 1 incorporates a stereocenter, however just racemic form of 1 is known so far. In order resolve compound 1 to enantiomers we have applied a kinetic resolution method assuming that the enantiomers would react with optically pure alcohols with different rates. (S)- and (R)-BILs bearing a bulky C2-symmetric binaphthyl fragment have been chosen as the chiral auxiliaries. We have shown that esterification of rac-1 with (S)-BIL in the presence of DCC DMAP afforded compound 2a in 75% yield and with diastereomeric ratio of 90:10. Accordingly, the diastereoselective reaction of rac-1 with (R)-BIL gave ester 2b as the major product (dr 87:13). Subsequent LiH-promoted re-esterification of BIL esters 2a or 2b with MeH followed by a basic hydrolysis of corresponding methyl esters 3a or 3b furnished optically enriched acids 1a or 1b (80% or 75% ee, HPLC data) [2]. The presence of the long-chained geranyl group in compound rac-1 appeared a key stereocontrolling factor that is crucial for a successful kinetic resolution of rac-1 to enantiomers 1a and 1b. An analog of compound rac-1 bearing the prenyl group instead of the geranyl unit at the stereogenic carbon atom generated with (S)-BIL corresponding (S)-BIL ester with poor diastereoselectivity (dr 60:40). References 1. B.B. Smirnov, G.V. Kryshtal, A.G. Konopljannikov, S.G. Zlotin, G.M. Zhdankina, RF Pat , Chem. Abstr., 2007, 147, S.G. Zlotin, G.V. Kryshtal, G.M. Zhdankina, A.A. Sukhanova, A.S. Kucherenko, B.B. Smirnov, V.A. Tartakovsky, Mendeleev Commun., 2014, ahead a print. 270

271 P160 SYTHESIS AD MASS-SPECTRA F LIGSACCHARIDE FRAGMETS F THE CAPSULAR PLYSACCHARIDE F STREPTCCCUS PEUMIA TYPE 3 AD THEIR EGLYCCJUGATES WITH BSA E.V. Sukhova 1, D.V. Yashynsky 1, Y.E. Tsvetkov 1, E.A. Kurbatova 2,.E. ifantiev Laboratory of Glycoconjugate Chemistry,. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Leninsky Prospect Mechnikov Research Institute of Vaccines and Sera, Russian Academy of Medical Sciences, Moscow, Malyi Kazennyi per. 5a Pneumococcal infection is a leading cause of death throughout the world [1] and a major cause of pneumonia, bacteremia, meningitis, and otitis media [2]. In the framework of a project directed to the design of a pneumococcal conjugated vaccine based on synthetic carbohydrate ligands, 3- aminopropyl glycosides of disaccharide fragments of the capsular polysaccharide of Streptococcus pneumonia type 3 have been synthesized. eoglycoconjugates of the synthesized oligosaccharides with bovine serum albumin (BSA) have been prepared by the squarate procedure. In the MALDI-TF mass-spectrum, a wide peak was observed with maximum at m/z 75733, which corresponds to inclusion into the conjugate of 19 disaccharide residues on average. The obtained results can be used for development of synthetic and semisynthetic pneumococcal polysaccharide vaccines and vaccines against various social diseases caused by encapsulated bacteria. References 1. Brien, K. L., Wolfson, L. J., Watt, J. P., Henkle, E., Deloria-Knoll, M., McCall,., Lee, E., Mulholland, K., Levine,. S., and Cherian, T. (2009) Lancet, 374, Weinberger, D. M., Harboe, Z. B., Sanders, E. A., diritu, M., Klugman, K. P., Ruckinger, S., Dagan, R., Adegbola, R., Cutts, F., Johnson, H. L., Brien, K. L., Scott, J. A., and Lipsitch, M. (2010) Clin. Infect. Dis., 51, This work was supported by the Russian Foundation for Basic Research, project o a 271

272 P161 SYTHESIS F LIGSACCHARIDE FRAGMETS F THE CAPSULAR PLYSACCHARIDE F STREPTCCCUS PEUMIA TYPE 14 AD THEIR EGLYCCJUGATES WITH BSA E.V. Sukhova 1, D.V. Yashynsky 1, Y.E. Tsvetkov 1, E.A. Kurbatova 2,.E. ifantiev Laboratory of Glycoconjugate Chemistry,. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Leninsky Prospect Mechnikov Research Institute of Vaccines and Sera, Russian Academy of Medical Sciences, Moscow, Malyi Kazennyi per. 5a Bacteria of the Streptococcus pneumoniae species are causative agents of severe inflammatory diseases of the respiratory tract, meningitis, otitis, bacteremia, etc.[1-3] that sometimes have lethal outcome[4]. In the framework of a project directed to the design of a pneumococcal conjugated vaccine based on synthetic carbohydrate ligands, 2-aminoethyl glycosides of tetra-, hexa- and octasaccharide fragments of the capsular polysaccharide of Streptococcus pneumonia type 14 have been synthesized. eoglycoconjugates of the synthesized oligosaccharides with bovine serum albumin BSA have been prepared by the squarate procedure. In the MALDI-TF mass-spectrum, a wide peak was observed with maximum at m/z 84342, which corresponds to inclusion into the conjugate of 18 hexasaccharide residues on average. The conjugate of the synthetic hexasaccharide with BSA was shown to possess of high antigenic activity comparable whit that for natural antigens of Streptococcus pneumonia type 14. This compound has demonstrated significant protective effect in experiments with mice infected by vital bacterial culture. Diagnostic pneumococcal test systems based on the pneumococcus synthetic capsular polysaccharide or on its fragments can be useful for avoiding shortcomings of natural polysaccharides, such as presence of admixtures, using living cultures of microorganisms, expensive methods of isolation and purification of antigens, and will result in creation of qualitatively new modern ELISA test systems. The findings can be used for development of synthetic and semisynthetic vaccines against pneumococcus and other socially important microorganisms possessing a polysaccharide capsule. References 1. Tatochenko, V. K. (2008) Zh. Detsk. Infekts., 2, Tatochenko, V. K. (2010) Zh. Mikrobiol., 5, Vishnyakova, L. A. (1993) Pulmonologiya, 3, Brien, K. L., Wolfson, L. J., Watt, J. P., Henkle, E., Deloria-Knoll, M., McCall,., Lee, E., Mulholland, K., Levine,. S., and Cherian, T. (2009) Lancet, 374, This work was supported by the Russian Foundation for Basic Research, project o a 272

273 P162 E-PT SYTHESIS F TRIAZLQUIAZLIES VIA CPPER CATALYZED TADEM CLICK AD ITRAMLECULAR C-H AMIDATI Ch.-M. Sun Department of Applied Chemistry, ational Chiao-Tung University, Hsinchu 300, TAIWA A novel and highly efficient copper catalyzed tandem synthesis of triazolo quinazolinones is explored. The synthetic strategy involves a sequential one-pot click reaction followed by aerobic intramolecular C-H amidation. Two distinct important transformations were carried out in one-pot by employing a single cost effective copper catalyst. The milder, rapid, oxidant and ligand free reaction conditions as well as broader substrate scope are the salient features of this novel protocol. 273

274 P163 PHARMACEUTICAL C-CRYSTALS F DIFLUISAL AD DICLFEAC WITH THEPHYLLIE A.. Surov, G.L. Perlovich G.A. Krestov Institute of Solution Chemistry RAS, , Ivanovo, Russia The development of pharmaceutical co-crystals is one of the hot topics in the field of crystal engineering nowadays as co-crystals can fine tune relevant physicochemical properties of active pharmaceutical ingredients (API). In this work, we report new co-crystals of nonsteroidal antiinflammatory drugs diflunisal (DIF) and diclofenac (DIC) with theophylline (THP) (Figure 1). According to the Biopharmaceutics Classification System (BCS), DIF and DIC belong to class II drugs with low solubility and high permeability as most SAIDs. Therefore, novel pharmaceutical co-crystals for DIF and DIC with enhanced physicochemical properties are still highly interesting. The co-crystals are characterized by single-crystal X-ray diffraction, differential scanning calorimetry (DSC) and solution calorimetry. In addition, analysis of crystal lattice energies of the co-crystals was done using PIXEL approach. Pharmaceutically relevant properties such as aqueous dissolution, intrinsic dissolution rate and relative humidity stability are also reported. In each structure, the asymmetric unit contains API and THP molecules connected by almost linear H hydrogen bonds involving the carboxylic acid of the API and an unsaturated atom of the imidazole ring of THP (acid-imidazole heterosynthon) In addition, the API forms the C-H contacts with the neighbouring THP molecule. The THP molecules are connected to each other by H hydrogen bonds to form centrosymmetric dimers that may be described in graph set notation as R 2 (10 ). 2 Figure 1. Therefore, both co-crystals have a similar organization of intermolecular hydrogen bonds to form a four-component supramolecular unit which consists of a THP centrosymmetric dimer and two APIs molecules. CSD survey and literature analyses show that analogous hydrogen bonded systems are quite common in THP co-crystals. PIXEL calculations reveal that crystal lattice energy of [DIC+THP] is higher than the one of [DIF+THP] on account of increased dispersion energy between the DIC molecules. The co-crystal formation enthalpies calculated from solution calorimetry experiments are small. It suggests that energies of hydrogen bonds in the co-crystals and pure components are comparable, and the packing energy gain is obtained mainly from weak van der Waals forces. The intrinsic dissolution studies (IDR) show that [DIF+THP] IDR is comparable to that of pure DIF. In case of [DIC+THP], the co-crystal form dissolution rate is found to be ca.1.3 times higher compared to the initial API. The aqueous dissolution profile of [DIF+THP] demonstrates a classical spring and parachute shape. For the [DIF+THP] co-crystal, a 5 hour time period corresponds to the spring phase. This is followed by a longer-term parachute phase, when slow crystallization and precipitation of the unstable DIF species occurs. The latter process lasts the following 25 hours. In case of [DIC+THP] system, the spring effect is not so evident. After 5-6 hours of dissolution, the concentration of [DIC+THP] co-crystal shows ca. 1.6 times the solubility of pure. Relative humidity experiments were conducted in order to compare the RH storage stability of the co-crystals to that of anhydrous theophylline. In contrast to THP, both co-crystals were stable at 100% RH. Further observations up to 2 months at 100% RH did not show any destruction or transformations of the co-crystals. This work was supported by a Grant from the President. МК and RFBR ( ). 274

275 P164 SYTHESIS AD LFACTRY PRPERTIES F UATURAL DERIVATIVES F LILAC ALDEHYDES P. Siska 1, P. Fodran 2, P. Szolcsanyi Slovak University of Technology, Department of rganic Chemistry, Bratislava, Slovakia 2 - Slovak University of Technology, Department of utrition and Food Assesment, Bratislava, Slovakia Lilac aldehydes 1 1 (Fig. 1) are naturally occurring monocyclic tetrahydrofuranyl terpenes considered as principal olfactory molecules of lilac flowers (Syringa vulgaris). We have designed, prepared and evaluated two sets of their unnatural racemic analogues as pure diastereomers. While the synthesis of gem-dimethyl homologues 2 7 starts from geranyl acetate, the preparation of methylene derivatives 8 10 commences from linalyl acetate. The key Lewis and/or Brønsted acid catalysed cyclisation furnishes easily separable cis-/trans-tetrahydrofuranyl esters as common advanced intermediates. The following functional group transformations lead to target aldehydes, alcohols, nitriles and olefins (Fig. 1). R geranyl acetate R R = H or Me or FG = C 2 Me, CH 2 H CH FG linalyl acetate CH, C, CH=CH 2 (1) (2-10) (Figure 1) The olfactory analysis revealed that while C-2 dimethylated homologues 2 7 exhibit similar herbal scents, the corresponding C-2 demethylated derivatives 8 10 possesses a broader range of scents with woody and/or flowery odours as dominant (Fig. 2). Unlike with homologues 2 7, the nature of C-1 substituent and/or relative stereochemistry has significant effect on the scent variations within the group of analogues Finally, our results suggest that both installation and removal of methyl group at C-2 significantly alters the olfactory properties of such unnatural derivatives 2 10 in comparison to their parent structures 1. CH vs. CH vs. CH (10) woody (1) flowery (Figure 2) (2) camphoraceous, minty, eucalypty [1] Wakayama, S.; amba, S. Bull.: Chem. Soc. Japan 1974, 47,

276 P165 DEVELPMET F REGISELECTIVE REDUCTIVE TRASFRMATI F 4,11-DIMETHXY-5,10-DIX-2- METHYLATHRA[2,3-B]FURA-3-CARBXYLIC ACID DERIVATIVES A.S. Tikhomirov 1,.A. melchuk 2, A.E. Shchekotikhin 1, M.. Preobrazhenskaya Gause Institute of ew Antibiotics RASM, Moscow, Russia 2 - Mendeleyev University of Chemical Technology of Russia,Moscow, Russia Previously, a series of linear furanoanthraquinones (anthra[2,3-b]furan-5,10-diones) was revealed as potent topoisomerase I poisons capable of inhibiting the growth of tumor cells including lines with activated mechanisms of multidrug resistance 1. However, for further structure-activity relation studies in a series of anthra[2,3-b]furan-5,10-diones the development of methodologies useful for the diversification at position 3 of this scaffold is necessary. In the present work, we have developed a new method of transformation of ethyl 4,11-dimethoxy-5,10-dioxo-2- methylanthra[2,3-b]furan-3-carboxylate 2 based on a selective reduction of carboethoxy group. Generally a direct reduction of carboethoxy group can be performed with strong reductive agents (LiAlH 4, abh 4, BH 3 -THF, etc.), but the presence of quinone moiety in ester 1 is limiting the application of these reagents. Therefore we choose a strategy for reduction of anthrafurandione-3- carboxylic acid derivatives via the corresponding chloroanhydride with mild reductive agents 3,4. As the first step, ethyl anthrafurandion-3-carboxylate 1 was transformed into chloroanhydride 2 by the basic hydrolysis and subsequent treatment with SCl 2 in refluxing benzene. Reduction of chloroanhydride 2 with diisobutylaluminium hydride (DIBAL-H) leads to the 3-hydroxymethyl- 4,11-dimethoxy-2-methylanthra[2,3-b]furan-5,10-dione (3) in low (5%) yield due to side the reduction of the quinone moiety. The unacceptable result encourages us for finding a more regioselective method of reduction of the chlorocarbonyl group in anthrafurandione 2. Hydrogenation of chloroanhydride 2 using Pd/BaS 4 or Pd/C as the catalyst in toluene gives 4,11-dimethoxy-2-methylanthra[2,3-b]furan-5,10-dione-3- carbaldehyde (4) in acceptable yield (57%). Reaction of anthra[2,3-b]furan-5,10-dione-3- carbaldehyde 4 with abh 4 in THF produces a high yield of the desired anthra[2,3-b]furan-5,10- dione-3-carbinol 3. The structures of the new anthra[2,3-b]furan-5,10-diones 2-4 were confirmed by methods of MR and high resolution mass-spectroscopy methods. 1. Shchekotikhin, A. E.; Glazunova, V. A.; Dezhenkova. Eur. J. Med. Chem. 2011, 46, Tikhomirov, A. S.; Shchekotikhin, A. E.Chem. Heterocycl. Compd. 2014, 50, Seyden-Penne, J, Reductions by the Alumino- and Borohydrides in rganic Synthesis, 2nd edition, Wiley-VCH, 1997, P Bai,.; Sha, Y.; Meng, G., Molecules, 2008, 13,

277 P166 STUDY F MECHAISMS F DI-, LIG- AD PLYMERIZATI REACTIS F ALKEES BY SYSTEMS BASED PHSPHIE AD α-diimie ICKEL CMPLEXES Yu.Yu. Titova 1, L.B. Belykh 2, F.K. Schmidt Irkutsk State University, Institute of il and Coal-Chemical Synthesis, Irkutsk, Russia 2 - Irkutsk State University, Chemical Department, Irkutsk, Russia Catalysis of lower alkenes (C 2 -C 4 ) dimerization by nickel complexes is the subject of great number of research for over four decades. At the present time there are several points of the nature view of the catalytically active site in the process of di-, oligo-and polymerization of lower alkenes. The most experimental justified concept is based on the decisive contribution to the catalytic process of hydride complexes i (II), formed by the interaction of nickel (II) with an organoaluminum compound are the most experimentally validated [1]. n the other hand, there are other points of view, is not always justified experimentally. Here, we report the results of study of the interaction mechanism between compounds of catalytic systems based on phosphine and α-diimine complex of i(0), i(i) and i(ii), with general formulas i(pph 3 ) 2 (C 2 H 4 ), i(pph 3 ) n Cl (n = 2, 3), ibr 2 (DAD-iPr or CH 3 ), i(dad-ipr or CH 3 ) 2 (DAD(-iPr) = 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene, DAD(- CH 3 ) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene), with Lewis acids (AlEt 3, AlEt 2 Cl, AlEtCl 2, B(F 5 C 6 ) 3, BF 3 Et 2 ), the role of alkenes in the formation of catalytically active species, and catalytic properties of these systems in a di-, oligo- and polymerization reactions of lower alkenes. During the study characteristics of the individual catalytic nickel complexes and systems based on this complexes in combination with Lewis acids were determined in the process of oligomerization of ethylene. For systems based on phosphine complexes of i(0) and i(i) by physical and chemical methods of research (MR-, EPR-, IR-spectroscopy) it was determined, that i(ii) complexes with an active i C bond produced by interaction of starting components initiate dimerization and oligomerization via the hydride mechanism. Investigation of the interaction between components of systems based on α-diimine complexes of i(0) and i(ii) by EPR spectroscopy establish the existence of equilibrium between the complexes i(i)[dad(-ipr)], i + [DAD(-iPr)] - and the radical-anion bound to Al- or B-atoms [2]. In the presence of substrate, this equilibrium shifts to the side of the radical-anion. Moreover, the part of radical-anion associated with aluminum or boron is increases when the acidic properties of Al- and B-containing co-catalysts are weakening. The EPR monitoring of α-diimine systems based on i(0) and i(i) complexes proves that direct relationship between the activity in the polymerization of ethylene and concentration of paramagnetic particles is absent. Perhaps, paramagnetic particles of i(i) play the same function in the regeneration of i(ii) active alkyl complexes, as in modified phosphines systems [3]. This work was supported by Russian Foundation for Basic Research ( mol_а) and a base part of Government Assignment for Scientific Research from the Ministry of Education and Science, Russia ( 2014/51,project code:627). Authors gratefully acknowledge Irkutsk Supercomputer Center of the Russian Academy of Sciences [1] Shmidt, F.K., Kataliz kompleksami metallov pervogo perekhodnogo ryada reaktsii gidrirovaniya i dimerizatsii (Hydrogenation and Dimerization Catalyzed by Complexes of First Row Transition Metals), Irkutsk: Irkutsk. Gos. Univ., [2] Actual problems of magnetic resonance and its application: Abstracts of XVII International Youth Scientific School. Kazan: P.136. [3] Yu.Yu. Titova, L.B. Belykh, A.V. Rokhin,.V. Soroka, F.K. Schmidt, Kinet. Catal., 55 (2014)

278 P167 XAS (XAES & EXAFS) FR CHARACTERIZATI F METAL- RGAIC FRAMEWRKS.P. Tkachenko 1, V.I. Isaeva 1, E.V. Belyaeva 1, W. Grunert 2, L.M. Kustov IC RAS, Lab.14, Moscow, Russia 2 - RUB, Lehrstuhl fur Technische Chemie, Bochum, Germany Recently, an approach, which incorporates functional cartridge molecules that are non-covalently bound within MFs has been demonstrated [1]. The goal of the present work is the purposeful design of the composite materials comprising analogs of Zn-MF-5 and Pd as advanced catalytic systems. The palladium was introduced via impregnation or CVD methods. Transmission Zn K and Pd K X-ray absorption spectra were measured at the Hasylab X1 station (DESY, Germany) using a Si(111) double crystal monochromator. The spectra were recorded at 77 K in vacuum. Reference spectra were taken using standard reference compounds: Zn, Zn-foil, Pd and Pd-foil. Data analysis was performed with the software package VIPER [2]. The required scattering amplitudes and phase shifts were calculated by the ab initio FEFF8.10 code [3]. The fitting was done in the k- and r-spaces. The Zn K-edge XAES evidenced that zinc exists as Zn 2+ ions in all synthesized organic frameworks. Introduction of Pd has no impact on the Zn K XAES of MFs. From the literature [4] the shortest Zn-Zn distance in two nearest Zn 4 units of MFs-5 is ~ 3.78 Ǻ. The fitting results of Zn K EXAFS gives the real distance between two Zn atoms in our samples is ~3.20 Ǻ, which allows supposing the presence in our samples of some Zn species and/or MF frameworks interpenetrating each other like that observed in [5]. The introduction of Pd in samples results in the increase of the amount of interweaved cells. The Pd K-edge XAES evidenced that palladium exists in metallic state. The fitting results of Pd K EXAFS has shown that the stabilization of very small Pd nanoparticles could be achieved using the micro- and mesoporous metal organic frameworks as the host matrices. In some cases the bimodal distribution of Pd was observed. Both the preparation method and palladium precursor impact to Pd particles size. The activity of metal organic frameworks contained Pd was investigated in the liquid-phase hydrogenation catalytic reactions [6-9]. References [1] Z. Wang, S. M. Cohen, Chem. Soc. Rev. 38 (2009) [2] K.V. Klementiev, [3] A.L. Ankudinov, B. Ravel, J.J. Rehr and S.D. Conradson, Phys. Rev. B, 58 (1998) [4] R-Q. Zou, R-Q Zhong, M. Du, T. Kiyobayashi, Q. Xu, Chem. Commun., 2467 (2007). [5] Havicovic, M. Bjorgen, U. lsbye, et al. J. Am. Chem. Soc. 129 (2007)3612. [6] V.I. Isaeva,.P. Tkachenko, I.V. Mishin, E.V. Afonina, G. I. Kapustin, L.M. Kozlova, W.Grunert, L.M. Kustov, Studies in Surface Science and Catalysis, 175 (2010) 707. [7] V.I. Isaeva, A.L. Tarasov,.P. Tkachenko, G.I. Kapustin, I.V. Mishin, C.E. Solov eva, L.M. Kustov, Kinetics and Catalysis 52 (2011) 94. [8] V.I. Isaeva,.P. Tkachenko, E.V. Afonina, L.M. Kozlova, G.I. Kapustin, W.Grünert, S.E. Solov eva, I.S. Antipin, L.M. Kustov, Microporous and Mesoporous Materials, 166 (2013) 167. [9] E.V. Belyaeva, V.I. Isaeva, E.E. Said-Galiev,.P. Tkachenko, S.V. Savilov, A.V. Egorov, L.M. Kozlova, V.Z. Sharf, L.M. Kustov, Russ. Chem. Bull. 2 (2014)

279 P168 CMPARIS F s, d AD f-elemets CMPLEXATI ABILITY WITH PEDAT PHSPHRYLATED AZACRW ETHER G.S. Tsebrikova 1, V.E. Baulin 1, I.. Polyakova 2, I.S. Ivanova 2, E.. Pyatova 2, A.Yu. Tsivadze Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow, Russia 2 - Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia ew ligands searching for selective binding of biologically active metal cations and radionuclides is a quite actual problem. Appending different phosphoryl containing substituents to the azacrown molecules is a promising approach to the new effective chelators design. ew complexes of, -bis(diphenylphosphorylmethyl)-4,13-diaza- 18-crown-6 (L) [ML](Cl 4 ) 2, where М 2+ = Zn, Cu, Co and i, are P h 2 ( )P P ( )P h 2 synthesized. Its composition is confirmed by elemental analyses and IR-spectroscopy data. The crystal structure of L and [CuL](Cl 4 ) 2 is determined by X-ray diffraction. L As a result of copper complex formation the macrocycle conformation changes. Two nitrogen atoms in the free ligand deviate from the average oxygen atoms plane to the one side, and in the copper complex to the different sides. The copper atom has surrounding in the shape of asymmetrically prolated tetragonal bipyramide [2+2О(Р)]+2. Comparison of the structure of [CuL](Cl 4 ) 2 and complexes [al](cs) [1] and [ErL(H 2 )( 3 ) 3 ] [2] is made. 1. A.Yu. Tsivadze, V.E. Baulin,.M. Logacheva, L.Kh. Minacheva, I.S. Ivanova, V.S. Sergienko, Zh. neorg. khim., 2007, 52, 2, L.Kh. Minacheva, I.S. Ivanova, I.K. Kireeva, V.E. Baulin, V.G. Sakharova, A.Yu. Tsivadze, V.S. Sergienko, Zh. neorg. khim, 2000, 45, 2, The work was financially supported by the Russian Foundation for Basic Research (Grants and ) 279

280 P169 SYTHESIS F ZIC AD CPPER CMPLEXES WITH ETHYLEEDIAMI-,-DI-3-PRPIIC ACID.V. Tsirulnikova 1,.. Podmareva 2, E.S. Dernovaya 1, I.V. Ananev 3, V.V. Podgorsky Federal State Unitary Enterprise «Research Institute of Chemical Reactants and Ultrapure Compounds (IREA)» 2 - Federal Medical & Biological Agency SRI of Physical-Chemical Medicine 3 - A.. esmeyanov Institute of rganoelement compounds Russian Academy of Sciences Zinc and copper complexes of carboxyl and phosphorus containing complexons are known as source of zinc and copper in chelate form. To expand the sources of zinc and copper in the form of chelates, which are used in various fields of science, medicine, pharmaceutics, agriculture and others, new compounds zinc and copper complexes of ethylenediamin-,-di-3-propionic acid (aseddp) were obtained. ew substances and method of their synthesis are suggested. The method is based on interaction aseddp with oxides of corresponding cations on the following scheme:, M=Zn, Cu Structures of synthesized compounds M(asEDDP) were confirmed by elemental analyses, MR and IR spectroscopy data, X-ray structure analysis. Ethylenediamin-,-di-3-propionic acid was synthesized by destruction of (ethylenediamine-,di-3-propionato)zinc(ii) dichloride (Zn(asEDDP)Cl 2 ), which was obtained by interaction zinc chloride, ethylenediamine and acrylic acid [1]. Based on 1 Н MR spectroscopy of a samples of the reaction mass, received during process of obtaining Zn(asEDDP)Cl 2 with template synthesis and installed for the first time crystal structure of dichlor(ethylenediamine)zinc(ii) the matrix of template synthesis, the mechanism of the formation aseddp was suggested. Destruction of the Zn(asEDDP)Cl 2 was carried out with chromatographic column filled by cation exchange resin KU-2-8 in H + form; elution was carried out with aqua ammonia. Using 1 H MR spectroscopy and paper electropherography was shown that the process of obtaining aseddp in alkaline conditions is accompanied by decarboxylation to form a mixture of acrylic acid, ethylenediamin--3-propionic acid and low-grade ethylenediamine of by the method of ion exchange. The newly synthesized derivatives can show promising biological activity. It is well-known that complexes of Cu are able to take part in combination therapy and realize effective correction of socially important neurodegenerative pathologies by means of regain disturbed homeostasis of Cu(II). Also, the obtained complex of Zn may be of interest as potential insulinomimetic substances. It will be tested in Scientific-educational center of applied chemical and biological research at Perm state Polytechnic University. [1] Podmareva.., Tsirulnikova.V., Fetisova T.S., Starikova Z.A. Method of synthesis of asymmetric ethylendiamine-,-dipropionic acid. Patent from

281 P170 THE SEVERAL ATIBITICS PRDUCED BY EXPERIMETAL STRAI STREPTMYCES RSEFLAVU WERE STUDIED BY MR SPECTRSCPE AD FFERED THE MST LIKELY STRUCTURES D.E. Tsvetkov 1, A.S. Shashkov 1, А.О. Chizhov 1,.A. Lapchinskaya 2, V.V. Kulyaeva 2, G.B. Fedorova 2, A.S. Trenin 2, E.G. Gladkikh 2, V.V. Pogozheva 2, M.. Makarova 2, G.I. rlova 2, G.S. Katrukha 2,.E. ifantiev D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences 2 - Gause Institute of ew Antibiotics at RAMS, Bolshaya Pirogovskaya, 11, Moscow, Russia In the course of screening for new antibiotics producing breeding methods was selected strain Streptomyces roseoflavus producing several macromolecular glycopeptide compounds whose structure comprises a chain of amino acid residues and carbohydrate residue. Antibiotics in this group have activity against gram-positive bacteria and mycobacteria, including Mycobacterium tuberculosis. These compounds were isolated from the culture by extraction with organic solvents, and then purified by HPLC method. Their structures were studied by mass spectrometry and 1 H MR and 13 C, CSY, HMBC, RESY correlation spectroscopy. n the base of the data obtained some assumptions were made about the possible structures of the active components. 281

282 P171 Pd(0)-CATALYZED DIASTERESELECTIVE HYDRGEATI F 3- METHYLIDEE-2-[(1S)-1-PHEYLETHYL]ISIDLI-1-E I C 2 - CTAIIG MEDIA Zh.R. Sagirova, I.V. Kuchurov,.V. Turova, E.V. Starodubtseva, S.G. Zlotin, M.G. Vinogradov Zelinsky Institute of rganic Chemistry Supercritical C 2 attracts considerable interest as a solvent for organic synthesis due to its accessibility and convenience for green chemistry. In this context, an effective environmentfriendly methodology for Pd-catalyzed diastereoselective hydrogenation of 3-methylidene-2-[(1S)- 1-phenylethyl]isoindolin-1-one (1), a model heterocyclic substrate incorporating a chiral inductor, has been elaborated. According to that, the C 2 -expanded ionic liquid (IL) containing the dissolved substrate and dispersed Pd (palladium acetate was used as a catalyst precursor) is a preferable reaction system for this transformation. High values of conversion (~100%) and diastereoselectivity (80% de) have been attained when the reaction was carried out in a three-phase system composed of scсо 2, СО 2 -expanded solution of 1 in [bmim] + Tf and Pd(0). Surprisingly, in the absence of C 2 the conversion was significantly worse. Ph H 2 /Pd Me C 2 -expanded * CH ionic liquid 2 Me Ph Me C 2 -containing medium Conversion (%) de (%) [bmim] + Tf 10 [bmim] + Tf СО [bmim] + BF 4 СО [bmim] + PF 6 СО bmim - 1-butyl-3-methylimidazolium, molar ratio [IL]/[1] = 6, [1]/[Pd(Ac) 2 ] = 50, p(h 2 ) = 20 аtm, p(total) = 120 atm, 50 C, 2 h. 282

283 P172 VEL ICKELACARBRAES BASED ID-5,6- DICARBADECABRAE A.P. Tyurin, A.Yu. Kostyukovich, E.V. Balagurova, I.V. Pisareva, A.F. Smol yakov, F.M. Dolgushin, I.T. Chizhevsky A..esmeyanov Institute of rganoelement Compounds of the RAS, 28 Vavilov Street, , Moscow, Russian Federation As part of our systematic work on the reactivity studies of metallacarboranes of transition metals with middle-cage carborane ligand based on nido-5,6-dicarbadecaborane (1), we synthesized and characterized three novel types of nickelacarborane clusters: closo-3,1,2-{ic 2 B 7 } (2 and 4), isonido-1,2,4-{ic 2 B 8 } (3) and closo-1,2,3-{ic 2 B 8 } (5) (Scheme 1). Scheme 1 The X-ray diffraction study of 2 revealed unusually long B(6)-B(9) distance of 2.000(6) Å. Quantum-chemical calculations on DFT B3LYP/Gen (Gen G** for atoms C, H, B, P and Dgdzvp for i) of its geometry were performed and, on this basis, the topology of electron density distribution using Bader s AIM (Atoms in Molecules) theory [1] was analyzed. The results of the calculations suggested that there are no bond critical points (BCP) (3; -1) between atoms B(6)-B(9) as well as between some other pairs of atoms such as i(2)-c(3), i(2)-b(5); B(4)-B(5), B(6)-B(7); B(8)-B(9) and B(7)-B(8). Ring critical points (RCP) (3; +1) of four-membered faces, which do not include metal atom, are characterized by negative Laplacian values (from to a.u.) with electron density in BCP and RCP of the polyhedron having close values. Analogous calculations for the other known in the literature closo-2,1,6-{ruc 2 B 7 } model, 2,2,2-(PH 3 ) 3-2,1,6- closo-ruc 2 B 7 H 9 [2], show quite similar distribution of critical points thus indicating significant electron delocalization over the polyhedral surface in both structures. 1. Bader R.F.W. Atom in Molecules. A Quantum Theory, Clarendon Press, xford, UK, 1990, Bould J., ro L.A., Macías R., Kennedy J.D., Londesborough M.G.S. Polyhedron. 2011, 30, Supported by the Russian Foundation for Basic Research (Project o ). 283

284 P173 CHEMICAL TRASFRMATIS F ALICYCLIC EPXIDES.V. Vereshchagina, T.. Antonova, S.A. Solovyovа Yaroslavl State Technical University, Yaroslavl, Russia The alicyclic epoxides are the basis for obtaining oxygen-containing compounds of different functionality (alcohols, ketones, diols, aliphatic dicarboxylic acids). The appropriate catalyst allows to obtain these compounds with high yield in the result of complex chemical transformations source epoxides with the formation of an intermediate complexes of various structure. Transformation of dicyclopentene epoxide (3,4-epoxitricyclo[ ]decane) are of particular interest for research [1, 2]. The reactivity of alicyclic epoxides of various structure (C 8 C 10 ) in process of isomerization in appropriate ketones with the use of catalysts Lewis acids has been investigated in this work. It is shown that the presence of double bonds in the cycle increases the reactivity of molecule epoxide C 8. The isomerization unsaturated 5,6-epoxy-cis-cyclooctene leads to unsaturated ketone 4-transcyclooctene-1-one with good yield. By-products have been obtained using solvents in process of isomerization. Selective formation specific ketone takes place only in the absence of solvent. The results of kinetic researchs and the availability of induction period of isomerization reactions indicate that the possible mechanism of the formation of the ketones includes donor-acceptor interaction between the molecule catalyst and epoxide with the formation of an intermediate complex II, as slow stage of process: I H H H al + Li II H H H al Li III + H H H al Li IV H H Li H al V H H + Li H al The redistribution of the electron density inside the complex II leads to a weakening the bond C-H and C- of reactive molecule epoxide. The sequential heterolytic breakup these bonds flowing through formation of intermediate complexes III IV, accompanied by the shift of proton and leads to the disclosure of epoxy cycle with formation unsaturated ketone. 1 Vereshchagina,.V. Alternative Methods for Production of Alicyclic Epoxides /.V. Vereshchagina, T.. Antonova, I.G. Abramov, G.Yu. Kopushkina // Petroleum Chemistry 2014, Vol. 54, o. 3, P Antonova, T. Catalytic Hydrogenation of Dicyclopentadiene to Dicyclopentene in the Liquid Phase / T.. Antonova, I.A. Abramov, V.Sh. Feldblyum, I.G. Abramov, A.S. Danilova // Petroleum Chemistry. 2009, Vol. 49, o. 5, P

285 P174 ELECTRCHEMICAL SYTHESIS F GERMAIUM ALKXIDES A.. Vereshchagin, M.. Elinson, I.V. Krylova, M.P. Egorov. D. Zelinsky Institute of rganic Chemistry, Moscow, Russia The wide applications of metal alkoxides, in particular in the preparation of various industrial oxide materials, make the development of improved techniques for their production an urgent task. The current methods of synthesis of M(R) n, where n exceeds 2 are mostly based on exchange reactions between MX n, (X may be Hal, R, H, R 2, (SiMe 3 ) 2 etc.) and alkoxidizing reagents. 1 These reactions are multistep processes and the starting materials are difficult of access. In addition, they involve various by-processes which contaminate the products and decrease their yields. For these reasons, the direct electrochemical synthesis of metal alkoxides by anode dissolution of metals in absolute alcohols in the presence of a conductive admixture seems a very promising method. It is known few publications (mostly patents) devoted to the electrochemical synthesis of some metal alkoxides. 2-4 We have found that electrochemical dissolution of germanium anode in undivided cell in absolute alcohol in the presence of sodium acetate as electrolyte under argon atmosphere results in formation of germanium alkoxide. Electrolysis Ge Ge(Alk) 4 aac / AlkH EtMgBr H 2 S GeS % GeEt % A bubling of dry H 2 S through alcoholic solution of germanium alkoxide leads to germanium sulphide in 85-90% yields. Liquid germanium alkoxides were isolated by distillation of alcohol under argon atmosphere. Followed addition of ethyl magnesium bromide leads to formation of tetraethyl germanium in 50-60% yields. The developed electrochemical process represent a prominent one-step approach to germanium alkoxide. Finally, the developed procedure utilizes simple equipment and undivided cell, and is valuable from the viewpoint of environmentally benign synthesis and large-scale processes. References 1. D. C. Bradley, in Preparative Inorganic Reactions, Vol. 2, ed. W. Z. Jolly, Interscience, Patent DE A, H. Lehmkuhl, W. Eisenbach Liebigs Ann. Chem., 1975, Patent CA A1,

286 P175 MICRSIZED CERIUM CHLRIDE IS EFFECTIVE MICHAEL CATALYST V.A. Vil`, A.. Terent`ev, I.A. Yaremenko,.V. Bityukov. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences The Michael reaction provides a commonly used and efficient synthetic route to C C bond formation. The synthesis involves the coupling of C-nucleophiles with unsaturated compounds activated by an electron-withdrawing group. β-dicarbonyl compounds comprise one of the largest groups of C-nucleophiles. The latter are used to prepare products that are widely used in organic synthesis. In the present study, we found that microsized cerium chloride prepared from cerium chloride heptahydrate catalyzes the coupling of β-diketones with vinyl ketones. The reaction products, β,δtriketones, are used in the synthesis of cyclic peroxides exhibiting antiparasitic activity and a wide range of nitrogen-containing heterocyclic compounds, as well as oxabicyclic systems, which are natural product analogues with antiparasitic activity. It was found that the catalytic activity of cerium chloride widely used in organic chemistry depends on the preliminary thermal treatment. The results of the present study suggest that this effect can play a substantial role in the synthesis with the use of organocerium reagents. References 1. Terent ev A.., Vil V. A., Yaremenko I. A., Bityukov. V., Levitsky D.., Chernyshev V. V., ikishin G. I., Fleury F. Preparation of a Microsized Cerium Chloride-Based Catalyst and its Application in Michael Addition of β-diketones to Vinyl Ketones // ew J. Chem., 2014, 38,

287 P176 STERESELECTIVE SYTHESIS F THE PETASACCHARIDES RELATED T THE FUCIDA FRM BRW SEAWEED CHRDARIA FLAGELLIFRMIS D.Z. Vinnitsky,.E. Ustyuzhanina, V.B. Krylov,.E. ifantiev Laboratory of Glycoconjugate Chemistry,.D.Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia Anionic polysaccharides fucoidans from brown seaweeds possess the different types of biological activity such as anticoagulant, antithrombotic, anti-inflammatory, antiangiogenic and other activities. 1-3 Fucoidan chains are built up mainly of sulfated -L-fucopyranosyl residues, but the fine structure of these biopolymers varies depending on seaweed species and growth conditions. Such structural features as types of glycosidic bonds, degree and pattern of sulfation, presence of branches and non-fucose residues were found to influence on the biological effect of fucoidans. 1 To reveal the pharmacophores of fucoidans we perform the synthesis of the oligosaccharides related to these biopolymers from different brown seaweed species. Here we report the synthesis of the pentasaccharide 1 related to the fucoidan from the seaweed C. flagelliformis as well as its totally sulfated derivative 2. The target compounds are built up of three (1 3)- linked α-l-fucopyranosyl residues, the central of which bears disaccharide branch consisting of α-l-fucofuranosyl and α-dglucuronyl units. Carbohydrate skeleton assembling of 1 and 2 was performed using di- and monosaccharides 3-6. The block 6 was prepared by pyranoside-into-furanoside transformation 4 of the corresponding fucopyranoside precursor. All glycosylation reactions proceeded with high stereoselectivity due to the presence of stereocontrolling groups in structures of glycosyl donors. 1. Cumashi, A.; Ushakova,.A.; Preobrazhenskaya, M.E.; D'Incecco, A.; Piccoli, A.; Totani, L.; Tinari,.; Morozevich, G.E.; Berman, A.E.; Bilan, M.A.; Usov, A.I.; Ustuzhanina,.E.; Sanderson, C.J.; Kelly, M.; Rabinovich, G.A.; Iacobelli, S.; ifantiev.e. Glycobiology 2007, 17, Ustyuzhanina,. E.; Bilan, M. I.; Ushakova,. A.; Usov, A. I.; Kiselevskiy, M. V.; ifantiev,. E. Glycobiology 2014, 24, in press. 3. Pomin, V.H. Biochim Biopys Acta 2012, 1820, V. B. Krylov, D. A. Argunov, D. Z. Vinnitskiy, S. A. Verkhnyatskaya, A. G. Gerbst,. E. Ustyuzhanina, A. S. Dmitrenok, J. Huebner,. Holst, H.-C. Siebert,. E. ifantiev, 2014, submitted. 287

288 P177 THE CATALYTIC ACTIVITY F i-raey IT THE HYDRGEATI REACTI F PYRAZLIES L.I. Vlasova 1, V.A. Dokichev 1, V.D. Sitdikov 2, I.V. Aleksandrov 2, V. Yu. Gordeev 3, Yu. V. Tomilov Institute of rganic Chemistry, Ufa Scientific Center RAS; rganic Cchemistry; Ufa, Russia 2 - Ufa State Aviation Technical University, Department of Physics, Ufa, Russia 3 - Ufa State Aviation Technical University, Department of Engineering Technology, Ufa, Russia 4 -. D. Zelinsky Institute of rganic Chemistry RAS, Laboratory of Chemistry of Diazo Compounds, Moscow, Russia The catalytic hydrogenation of pyrazolines in the presence of i-raney that is proceeding with a rupture of - bond, is a convenient method of synthesis of 1,3-propylenediamines and 3- aminopyrrolidones, which exhibit the activity against of Alzheimer's disease, various tumors and cancer cells, and they are perspective as a antiarrhythmic drugs [1]. In the present work we investigated the hydrogenation reaction of pyrazolines different structure in the presence of i-raney and the effect of nature i-al alloy on the yield and the isomeric composition of the resulting 1,3-propylenediamines and 3-aminopyrrolidones. Experiments were carried out in a steel autoclave at 100 C and a hydrogen pressure of 75 atm in the presence of 10 wt.% catalyst. The exit of hydrogenation products was 55-97%. R 2 R 1 H 2 R 2 R 1 H 2 H 2 / i R 3 H H 2 / i R 1 = C 2 Me R 3 R 2 H 2 C H Figure 1. The image of nickel-aluminum alloy n an example of methyl 4-phenyl-4,5-dihydro-1H-pyrazole-3-carboxylate, it is shown, that the hydrogenation proceeds at a high yield (97%) and selectivity (ratio of cis- and trans-isomers of 1: 21) when using a i -Al alloy containing 49% ial 3 and 51% i 2 Al 3. -substituted pyrazolines, in the conditions chosen by us, do not react into the hydrogenation reaction. 1. Patent RU

289 P178 BIDIG F i(ii) IS T CHITSA AD ITS -HETERCYCLIC DERIVATIVES: THERETICAL AD EXPERIMETAL STUDY A.P. Portnyagin, S.Yu. Bratskaya, A.V. Voit Institute of chemistry FEB RAS, Vladivostok, Russia Fast expansion of chitosan application in the fields, where good chelation properties of polymers are required, has significantly promoted interest to experimental and theoretical investigations of metal ions interactions with native and chemically modified chitosans, and to the development of new procedures for synthesis of derivatives with increased sorption capacities and enhanced selectivity. While decades ago the main interest in this type of interactions was focused on the environmental application of chitosans for heavy metals recovery, now complexation of metal ions with chitosan and its derivatives is considered as an important stage in formation of metal nanoparticles in chitosan matrix for catalytic and optical applications. These interactions are also important for understanding of the mechanisms of antibacterial, antifouling, and antitumor activity of chitosan-metal complexes. There are two main coordination models of ion binding to chitosan: bridge model, which describes intermolecular coordination of metal ions with several amine groups, and pendant model, which describes binding of the metal ion to a single amine group as a pendant. The most favorable coordination model bridge or pendant is still disputable. In this work we present theoretical study of i(ii) ions binding to chitosan and its -heterocyclic derivatives with 4-pyridylethyl (PEC-4), 2-pyridylethyl (PEC-2) and imidazole (IMC) moieties, which now attract attention due to the wide range of their functional properties. Trends in energies of complex formation in dependence of type of functional substitute in chitosan found by DFT calculations have been compared with experimental data obtained in sorption experiments using a series of chitosan derivatives. It was shown that bridge complexes are more stable than pendant. Among the bridge models, structures that consist of substituted and unsubstituted chitosan residue are more stable than complexes that consist of two substituted residues. Substituted chitosan residues can be placed into the row according to their stability: IMC PEC- 2>PEC-4 ative. The higher stability of IMC and PEC-2 complexes with nickel can be assigned to the strong i- bonds with heterocyclic nitrogen and chelate effect. These factors are not fully implemented in the complexes of PEC-4 that s why there are no great advantages compared to native chitosan. The most stable complex is [i-imc 2 ] 2+. Analyzing the atomic charges it was shown that charges on oxygen atoms of hydroxyl groups, which are bonded to nickel cation, differ very small from each other and don t correlate with energy of complex formation. itrogen atom charges can be divided into 3 groups the highest charge on amine group atoms, a bit lower charge on imino group nitrogen atom and the lowest charge on heterocyclic nitrogen atoms. More interesting behavior is observed when nickel atomic charges are considered that elucidates the charge transfer from ligands to central ions. The relation between i charge and relative formation enthalpy is presented on Figure. The good correlation between these two parameters is obvious. Therefore one can make a conclusion that not only bonding atoms (, ) participate in charge transfer from ligands to central ion but other ligand atoms also play a role Qi, e H', kj/mol Dependence of the i ion effective charge on the relative enthalpy of complexes formation. 289

290 P179 SYTHESIS F FLURIATED BEZQUILES, APHTHYLPYRIMIDIES AD APHTHYLDIHYDRPYRAZLES BASED CHEMICAL TRASFRMATIS F 2,3 DIFLURAPHTHALEE.V. Volchkov, M.B. Lipkind, M.A. ovikov,.m. efedov.d. Zelinsky Institute of rganic chemistry of Russian Academy of Sciences, Leninsky prospect 47, , Moscow, Russian Federation For the purpose of search new biologically active compounds methods for the synthesis of fluorinated benzoquionolones with different fusion type of naphthalene and pyridone fragments (compounds 2-4) as new structural derivatives of fluoroquinolone antibacterial drugs were developed. Series of fluorine-containing 2-amino-4-naphthyl-6-arylpyrimidines (compounds 5-7) as potential antibacterial and antifungal substances were prepared. Fluorinated 3-naphthyl-5-aryl- and 3,5-dinaphthyl-4,5-dihydro-(1H)-pyrazoles (8-10) as cytotoxic compounds were also synthesized. C 2 H A r R F R 1 2 R = H, M e C H C lf C flo w F F F 5 F H 2 R 1 = E t, B z, cy clo - C 3 H 5 C 2 H R H F R F 3 C 2 H Z H F 4 Z =, C H 2, M e F 8 F A r M e 1 F F F F 9 A r M e F F F F A r H 2 H 2 A r M e A r Developed synthetic ways are based on common starting compound 2,3-difluoronaphthalene 1, prepared by соpyrolysis of CHCF 2 and styrene 1,2, and subsequent efficient introduction of various functional groups ( 2, R 2, C 2 H, CMe, CH) in different positions of 2,3- difluoronaphthalene structure. References 1).M. efedov, H.V. Volchkov. Mendeleev Comm., 2006, ).M. efedov, A.A.Ivashenko. USSR Inventor Certificate, 290,900,

291 P180 TRASITI METAL CATALYZED ARYLATI F PHSPHRYL- STABILIZED CARBAIS: A CVIIET APPRACH T α-fuctialized (ARYLMETHYL)PHSPHATES M.. Volkova, A.Y. Mitrofanov,.S. Goulioukina, I.P. Beletskaya Moscow State University, Department of Chemistry, Moscow, Russia (Arylmethyl)phosphonates containing electron-withdrawing group such as an ester, cyano, dialkoxyphosphoryl, or nitro group on the α-carbon are of considerable interest as versatile reagents for organic synthesis. These compounds are vital starting materials for the Horner Wadsworth Emmons reaction or the Michael addition and the presence of functional groups provides additional synthetic potential. In this study a series of α-functionalyzed (arylmethyl)phosphonates was synthesized under the Hurtley 1 reaction technique by the direct copper-catalyzed arylation of methanephosphonates, bearing additional EWG-group (C, CEt, P(Et) 2 ) (Scheme 1). Scheme 1. Copper-catalyzed arylation of α-functionalized methanephosphonates. It turned out that in each case a fine adjustment of catalytic system is necessary depending on the nature of functional group present. ptimization of the reaction conditions (ligand type, base, solvent, etc.), scope of aryl iodides used and possibility of further in situ product modification (e.g. Scheme 2) will be discussed. Scheme 2. ne-pot synthesis of α-functionalyzed phosphonates comprising quaternary α-c atom. We have also developed conditions for the palladium catalyzed cross-coupling of diethyl nitromethylphosphonate with aryl iododes. A key requirement was found to be the proper choice of phosphine ligand (Scheme 3). This work was supported by the RFBR (grant ) and was carried out in the framework of the International Associated French Russian Laboratory LAMREM. [1] I. P. Beletskaya, A. Yu Fedorov, Modern Copper-Catalyzed Hurtley Reaction: Efficient C- Arylation of CH-Acid Derivatives, in Copper-Mediated Cross-Coupling Reactions (eds G. Evano and. Blanchard), John Wiley & Sons, Inc., Hoboken, J, USA, 2013, ch

292 P181 A THERETICAL AD EXPERIMETAL STUDY F A UUSUALLY STRG HYDRGE BD I A SALICYLAMIDE CCRYSTAL A.V. Voronin 1, M.V. Vener G.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences 2 - D.Mendeleev University of Chemical Technology of Russia Solubility is one of significant parameters that have an impact on drug therapeutic effectiveness. At the present time, a new method to improving solubility by two-component crystal engineering has gained increased interest 1. These species, known more commonly as pharmaceutical cocrystals, consist of an active pharmaceutical ingredient and a second component which is safe for human consumption. If the second component is solid at ambient conditions, the terms a cocrystal and a salt are used. The latter term is referred to the species formed by ions, while the cocrystal denotes a complex of non-ionized molecules 2. The considered crystals usually consist of the H, C,, and F atoms. Therefore, the ionized molecules appear due to the intra- or intermolecular proton transfer. This phenomenon is associated with existence of the short (strong) hydrogen bonds (H-bonds) with energies larger than 60 kj/mol 3. The different strength of H-bonds in the salts and cocrystals leads to different properties of the resulting solid. The problem of obtaining the twocomponent crystal in desired ionization state is being widely studied in recent years 4. Adequate description of the structure and properties of the two-component crystals with strong H-bonds requires the combined use of the experimental and computational approaches. The new (2:1) cocrystal of a non-steroidal anti-inflammatory drug salicylamide with the oxalic acid is used as an object of the present study. According to the Cambridge Structure Database analysis, only 0.9% of all molecular complexes with ΔpK a of components > 4 form cocrystals instead of salts 5. ΔpK a equals to 7.14 for the cocrystal under consideration. According to single crystal X-Ray, the salicylamide cocrystal possesses an unusually short -H... intramolecular H-bond with... distance of Å. The pattern of noncovalent interactions has been quantified using the solid-state DFT computations (B3LYP/6-31G**) followed by the Bader analysis of the periodic electron density. The lattice energy of the cocrystal is evaluated in a way described in Ref. 6 to be equal to kj/mol. It is found that -H... and -H... hydrogen bonds provide nearly 70% of all lattice energy in crystal. The IR spectrum computed in the harmonic approximation using solid-state DFT agrees with the experimental spectrum of the crystal. The IR intensive band around 2400 cm -1 is caused by the stretching vibration of the H group, involved into formation of the short (strong) H-bond. [1] a) A.V. Trask, W.D.S. Motherwell, W. Jones. Physical stability enhancement of theophylline via cocrystallization. Int. J. Pharm. 2006, 320, b). Schultheiss, A. ewman. Pharmaceutical cocrystals and their physicochemical properties. Cryst Growth Des., 2009, 9(6), [2] F. Lara-choa, G. Espinosa-Pérez. Cocrystals Definitions. Supramol. Chem., 2007, 19(8), [3] T. Steiner, The Hydrogen Bond in the Solid State, Angew. Chem. Int. Ed. 2002, 41, [4] C.B. Aakeroy, M.E. Fasulo, J. Desper. Cocrystal or salt: does it really matter? Mol. Pharm., 2007, 4(3), [5] A.J. Cruz-Cabeza. Acid-base crystalline complexes and the pka rule. CrystEngComm, 2012, 14, [6] A.. Manin, A.P. Voronin,.G. Manin, M.V. Vener, A.V. Shishkina, A.S. Lermontov, G.L. Perlovich, Salicylamide Cocrystals: Screening, Crystal Structure, Sublimation Thermodynamics, Dissolution and Solid-State DFT Calculations, J. Phys. Chem. B, 2014, 118,

293 P182 XYPALLADATI-HECK TADEM REACTIS F ITERAL ALKYES WITH ALLYLIC ALCHLS: A EW APPRACH T ISCUMARIS AD BEZPYRAS M.-F. Zheng, W.-Q. Wu, H.-F. Jiang South China University of Technology, School of Chemistry and Chemical Engineering, Guangzhou, P. R. China Transition metal-catalyzed cascade reactions have emerged as a valuable approach for the synthesis of complex molecular structures and attracted great attention. 1 In this regard, the electrophilic activation of the alkynes by coordination to palladium continues to be a fascinating arena due to its high efficiency in constructing multiple new chemical bonds in one step. 2 Recently, a new approach for isocoumarins and benzopyrans between internal alkynes and allylic alcohols is developed. This one-pot cascade cyclization is supposed to go through a sequential intramolecular C bond cyclization, olefin insertion, β-h elimination and isomerization to afford the isocoumarin products, all occurring in a single operation. Remarkably, benzopyran derivatives could be also constructed efficiently via this cascade transformation (Scheme 1). Scheme 1 Reference: 1. (a) Waslike, J.-C.; brey, S. J.; Bake, R. T.; Bazan, G. C. Chem. Rev. 2005, 105, (b) Tietze, L. F. Chem. Rev. 1996, 96, 115. (c) icolaou, K. C.; Edmonds, D. J.; Bulger, P. G. Angew. Chem. Int. Ed. 2006, 45, (a) Frühauf, H.-W. Chem. Rev. 1997, 97, 523. (b) jima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96,

294 P183 EFFICIET SYTHESIS F PYRAZLES VIA CPPER-CATALYZED RELAY XIDATI STRATEGY X.-D. Tang, W.-Q. Wu, H.-F. Jiang South China University of Technology, School of Chemistry and Chemical Engineering, Guangzhou, P. R. China Pyrazoles are an important heteroaromatic ring for pharmaceutical industry. Selected pharmaceutical examples include the well-known drugs Mavacoxib, Celebrex, and Acomplia. Many methods have developed for this attractive scaffold, and the classical preparation method is the condensation of 1,3-dicarbonyl compounds and their 1,3-dielectrophilic equivalents with hydrazines. However, they often suffer from some drawbacks such as multi-step synthesis, long reaction time, use of expensive reagents, and the limitation of the substrates. In the past several years, oxime esters have become powerful tool for -heterocycles in presence of Cu catalysts. Based on our continue interest in oxime esters, herein, we present a Cu-catalyzed synthesis of 1,3- and 1,3,4-substituted pyrazoles from oxime acetates, anilines and formaldehyde (Scheme 1c). This process involves Cu-catalyzed - bond cleavage, C-C/C-/- bond formation and oxidative dehydrogenation process, which is a relay oxidation process and the oxidants are oxime acetates and 2. Scheme 1 References [1] Tang, X.; Huang, L.; Qi, C.; Wu, W.; Jiang, H. Chem. Commun., 2013, 49, [2] Huang, H.; Ji, X.; Tang, X.; Zhang, M.; Li, X.; Jiang, H. rg. Lett. 2013, 15, [3] Tang, X.; Huang, L.; Qi, C.; Wu, X.; Wanqing Wu, W.; Jiang, H. Chem. Commun. 2013, 49, [4] Tang, X.; Huang, L.; Xu, Y.; Yang, J.; Wu, W.; Jiang, H. Angew. Chem. Int. Ed. 2014, 53,

295 P184 SELECTIVE SYTHESIS F CYCLIC PERXIDES FRM TRIKETES AD H 2 2 I.A. Yaremenko, V.A. Vil`, I.B. Krylov, A.. Terent`ev. D. Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow, Russian Federation In the past decades, the chemistry of organic peroxides has attracted considerable attention from physicians and pharmacologists because these compounds were found to have antimalarial, antihelmintic, and antitumor activities. The interest in the synthesis of radical polymerization initiators and drugs gave impetus to the development of methods for the synthesis of peroxides with the use of carbonyl compounds, their derivatives, and H 2 2 as the starting reagents. A method for the assembly of tricyclic structures containing the peroxide, monoperoxyacetal, and acetal moieties was developed based on the acid-catalyzed reaction of β,δ-triketones with H 2 2. The tricyclic compounds are produced in 39 90% yields and can be easily isolated from the reaction mixture. The reaction is scaled up to several grams. The resulting tricyclic compounds are unusual in that they contain one acetal and two monoperoxyacetal moieties, which are as a rule unstable and can undergo peroxidation in the presence of water and hydrogen peroxide under acidic conditions, and acetals are susceptible to hydrolysis (Scheme 1). Scheme 1. Synthesis of Tricyclic Peroxides To assess the resistance of tricyclic peroxides to reagents used in organic synthesis and to determine the structures, which are interesting to test for biological activity, we performed the oxidation, alkaline hydrolysis, amidation, and reduction (Scheme 2). Scheme 2. Reactions of Tricyclic Peroxides Tricyclic monoperoxides showed high antischistosomal activity against Schistosoma mansoni. This work is supported by RFBR Reference Terent ev A.., Yaremenko I.A., Chernyshev V.V., Dembitsky V.M., ikishin G.I. // J. rg. Chem. 2012, 77, Terent'ev A., Yaremenko I.A., Vil' V.A., Dembitsky V.M, ikishin G.I. // Synthesis. 2013, 45 (2), Ingram K., Yaremenko I.A., Krylov I.B., Hofer L., Terent'ev A.., and Keiser J. // J. Med. Chem. 2012, 55 (20),

296 P185 EW LIGADS BASED XAMIIC ACID THIHYDRAZIDES V.. Yarovenko, E.S. Zayakin, I.V. Zavarzin, M.M. Krayushkin.D. Zelinsky Institute of rganic Chemistry, RAS, Moscow, Russia Convenient methods for the synthesis of poorly studied thiohydrazides of oxaminic acids 1 were developed. Compounds 1 are of special interest as complexing structures as containing donor atoms with both high (,) and low (S) electronegativity, due to which they can form fairly stable coordination compounds with both hard and soft Pearson s acids. ew ligands 2-7 were synthesized from oxaminic acid thiohydrazide derivatives. 1 R = Alk, Ar, Het R H S H 2 H R H H S 3 S H H R H S 4 S H R H H R1 R H H H H 2 H H H S H H R R2 R1 H R R H 296

297 P186 SYTHESIS F 8-H-PYRIMID[ 5,4-B] [1,4]-THIAZIE-5,5-DIXIDE DERIVATIVES M.A. Prezent, I.V. Zavarzin. D. Zelinsky Institute of rganic Chemistry, Laboratory for Chemistry of Steroid Compounds, Moscow, Russia We showed for the first time that methanesulfonylacetonitrile 1 can interact with two molecules of dimethylformamide acetal. The reaction proceeds at both methylene and methyl groups of 1 to form condensation product 2. The latter smoothly reacts with binucleophiles, such as acetamidine and guanidine to form new representatives of the pyrimidine series: 4-amino-5-sulfonylpyrimidines 3а,в,с. S 1 DMA DMFA S 2 nucleophile S 3a-c R S 4a-c R R = H (a); Me (b); H 2 (c) Heating of 3а,в,с in acetic acid results in heterocyclization to form bicyclic systems 4а,b,c. ew 4-amino-5-sulfonylpyrimidines 3а,в,с were thus obtained, as well as derivatives of earlier undescribed system 8H-pyrimido[4,5-b] [1,4]-thiazine-5,5-dioxide 4а,b,c. 297

298 P187 A CRUCIAL RLE FR THE ESCHERICHIA CLI S4 -ATIGE - ACETYLATI I THE BACTERIPHAGE G7C RECEPTI E.L. Zdorovenko 1,.S. Prokhorov 2,.G. vchinnikova 1, A.S. Shashkov 1, A.V. Letarov 2, Y.A. Knirel D.Zelinsky Institute of rganic Chemistry, Russian Academy of Sciences, Moscow, Russia 2 - S.. Vinogradsky Institute of Microbiology, Russian Academy of Sciences, Moscow, Russia The phage host system E. coli 4s bacteriophage G7C was isolated from horse feces in Despite an extremely narrow host range, E. coli 4s being the only known G7C host, the phage persisted in the same horse population for several years. Evaluation of the fine mechanisms of the G7C interactions with the host cell is important for understanding this ecological phenomenon. Studies of G7C adsorption proteins suggested that the bacterial lipopolysaccharide is the primary phage receptor. In this work, we studied structure and genetics of biosynthesis of the polysaccharide chain of the lipopolysaccharide (-antigen) in wild type E. coli 4s and its G7C-resistant mutants 4sI-2 and 4sI-4 that kept the ability to produce a long-chain -antigen. The 4s -antigen was found to be related to that of E. coli 22 differing only in decoration of the linear polysaccharide with an -D-Glc group on GlcA. The -antigen of both mutants had the same structure as that of the wildtype strain but lacked -acetylation on GalAc. E. coli 4s and 22 possessed essentially identical -antigen gene clusters, which included all genes that were necessary for biosynthesis of the E. coli 22 polysaccharide, including a gene for the -acetylation of GalAc called wclk. In addition, E. coli 4s, but not E. coli 22, had a three-gtr gene operon that was putatively responsible for the glucosylation of the -antigen. In both 4sI-2 and 4sI-4 mutants, the wclk gene was inactivated by an insertion of a IS1-like element, the genetic basis that accounted for the lack of the -antigen -acetylation. Complementation of the mutants with the wclk gene from E. coli 4s restored the phase-sensitive phenotype. The data obtained demonstrated that the -antigen of E. coli 4s is the specific receptor of bacteriophage G7C and the -antigen -acetylation is necessary for the phage reception. 298

299 P188 EW WAYS T HALPERXIDES A.T. Zdvizhkov, A.. Kulakova, R.A. Pototskiy, P.S. Radulov, A.. Terentev, G.I. ikishin.d. Zelinsky Institute of rganic Chemistry, RAS, Laboratory for Studies of Homolytic Reactions, Moscow, Russia rganic peroxides are one of the most useful classes of organic compounds in different part of human life. The most common application of these substances is polymer chemistry. Moreover, the high anticancer and antihelminthic activities have been discovered recently. It makes researchers invent new types of peroxides and new ways to them. Substitution of halide atom seems huge part of organic synthesis. So we focused on synthesis of halide-substituted peroxide. The system of I 2 /hydroperoxide was examined in addition to double C=C bond reaction. It was found that type of product depends on I 2 -hydroperoxide ratio. oteworthy target iodoperoxides were obtained with huge excess of iodine. However, iodoalcohol as side product formed inevitably. This fact may be complained by cleavage of - moiety under iodide-anion action. To avoid degradation of target product we suggested use -halosuccinimides as halogenations agents. The decision allows decrease of haloalcohol percentage. However, it have been founded employment of -halosuccinimides initiate a new reaction of radical halogenations of double C=C bond. The problem was solved with adding of catalytic amounts of phosphomolibdic or phosphotungstic acids. Described results have extremely value. Developed methods allow to synthesis wide number of structures containing different halogen atoms and peroxide moiety. This work was supported by the Russian Science Foundation (Grant ). 299

300 P189 MDELIG METAL-CATALYZED CRSS-CUPLIG AD ADDITI REACTIS USIG CMBIED QUATUM AD MLECULAR MECHAICS METHDS A.A. Zeifman, F.. ovikov,.v. Stroganov, V.S. Stroylov, I. Yu. Titov, G.G. Chilov, I.V. Svitanko, V.P. Ananikov. D. Zelinsky Insitiute of rganic chemistry, Moscow, Russia We have developed a combined QM + MM FEP (free energy perturbation) protocol for modeling metal-catalyzed reactions in explicit solvent media. First, QM calculations are employed to handle reagent, transition state and product in vacuum, and then MM FEP is used to account for solvation effects. In contrast to commonly used PCM, MM FEP allows to obtain a true solvation free energy by accounting for all solvent-solute interaction at atomic level and by thermodynamic averaging over entire statistical ensemble and thus potentially offers great advantages in precision of calculations (standard error <1 kj/mol) and comprehension of the entire process. Proposed method was employed to study the free energy profile of the model reaction (final step of Suzuki-Miyaura cross-coupling) in 5 different solvents (benzene, toluene, ethanol, DMF, water). Trend in activation free energy change among solvents predicted by our method was in accordance with conventional PCM calculations, but for total reaction free energy change quantitative disagreement was observed. Detailed analysis revealed that Pd(PPh 3 ) 2, the final Pd-containing product of reaction, formed energetically favored hydrogen bonds in water and ethanol which were explicitly accounted by MM FEP but omitted in PCM calculations. 300

301 P190 CPPER-CATALYZED ALLYLATI F HEM-DIFLUR- SUBSTITUTED RGAZIC REAGETS A.A. Zemtsov, V.V. Levin, A.D. Dilman, M.I. Struchkova. D. Zelinsky Institute of rganic Chemistry, Moscow, Russia The ability of CF 2 -fragment to serve as a bioisostere of ether oxygen or a carbonyl group attracted great attention in medicinal chemistry. 1,2 Several methods for the synthesis of the compounds, containing difluoromethylene fragment, such as direct deoxofluorination of carbonyl group 3 or consecutive transformations of halodifluoromethyl ethers 4 are already well-described. However, these methods suffer from a number of disadvantages, including hazardous reagents (SF 4, DAST) or inefficiently long synthetic sequences. Recently we formulated a novel strategy for assembling gem-difluorinated products from three independent components: nucleophile, electrophile and difluorocarbene 5. We developed an extension of this methodology by using organozinc reagents as nucleophiles and allyl halides as electrophiles in a one-pot consecutive manner. 6 rganozinc halides are involved into the reaction with difluorocarbene generating difluorinated organozinc reagents. The latter species undergo regioselective allylation reaction in the presence of catalytic amount of copper (I) salt. This reaction provides a convenient route to the different CF 2 -containing olefins by a formation of two C-C bonds in a one step. This work was supported by Russian Foundation for Basic Research ( mol_a). 1. Fluorine in Medicinal Chemistry and Chemical Biology; jima, I., Ed.; Wiley: Chichester, U.K., Meanwell,. A. J. Med. Chem. 2011, 54, Al-Maharik,.; Hagan, D. Aldrichimica Acta 2011, 44, Qing, F.-L.; Zheng, F. Synlett 2011, Levin, V. V.; Zemtsov, A. A.; Struchkova, M. I.; Dilman, A. D. rg. Lett. 2013, 15, Zemtsov, A. A.; Kondratyev,. S.; Levin, V. V.; Struchkova, M. I.; Dilman, A. D. J. rg. Chem. 2014, 79,

302 P191 Cu-CATALYZED ARYLALKYLATI F C-C DUBLE BDS: A EFFICIET RUTE T ALKYL SUBSTITUTED XIDLES Y. Yu, M. Zhang, H.-F. Jiang School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou , P. R. China Transition metal-catalyzed intramolecular or intermolecular oxidative difunctionalization of alkenes has attracted more and more attention in recent years, since the introduction of diverse functional groups into organic molecules can lead to lots of important innovations for synthetic chemistry. Upto-date researches presented that copper was an efficient, abundant, and inexpensive metal to perform these reactions instead of rhodium, ruthenium or palladium catalysts. Compared with C-, C-, C-Br bond formations, dicarbonation of C-C double bonds is less reported since a final C-H cleavage is required. [1-3] In order to expand the richness of copper-catalyzed difunctionalization of alkenes, we focus on the study of dicarbonation of C-C double bonds. We herein report an efficient and highly regioselective strategy for the construction of alkyl substituted oxindoles through the copper-catalyzed oxidative annulation between potassium alkyltrifluoroborates with -arylacrylamides (Scheme 1). It was supposed that potassium alkyltrifluoroborate should be an alkyl radial precursor and played an important role in this transformation. Scheme 1 References [1] Huang, L.; Qi, C.; Liu, X.; Jiang, H. J. Am. Chem. Soc. 2010, 132, [2] Wang, Y.-F.; Zhu, X.; Chiba, S. J. Am. Chem. Soc. 2012, 134, [3] Bovino, M. T.; Chemler, S. R. Angew. Chem. Int. Ed. 2012, 51,

303 P192 VERSATILE SYTHESIS F QUILIES FRM α-2-itraryl ALCHLS AD ALCHLS VIA RUTHEIUM-CATALYZED HYDRGE TRASFER STRATEGY F. Xie, M. Zhang School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou , P. R. China In line with the principle of green chemistry, the application of abundant and sustainable alcohols as both hydrogen suppliers and coupling components via hydrogen-transfer strategy is, in synthetic chemistry, of important significance. 1 Quinoline derivatives constitute a significant important class of nitrogen-containing heterocycles. To date,a large number methods have been developed to access various quinolines. However, many of these methods suffer the use of special pre-functional or less environmentally benign halogenated reagents, which would increase the complexity of the work-up procedure or result in detrimental influence on environment. 2 Hence, the exploration of straightforward methods for quinoline syntheses from easily available and eco-compatible reagents still remains a demanding goal. Herein, we report a new and straightforward method for versatile synthesis of quinoline derivatives from stable and easily available α-2-nitroaryl alcohols and alcohols via ruthenium-catalyzed hydrogen transfer strategy. In such as a synthetic protocol, two alcohol units and the nitro-group serve as the hydrogen donors and hydrogen acceptor, respectively. Hence, there is no need for the use of specialized reducing agents. By employing Ru 3 (C) 12 /dppf/t-buk as an efficient catalyst system, various substituted products can be furnished in reasonable to good isolated yields. The transformation is operationally simple and there is no need for pre-functionalization (Eq.1). R 1 R 2 R 3 Hydrogen donors H H R 5 + R 4 R 5 Ru cat (Eq.1) R 2 R 3 4 Hydrogen acceptor Scheme 1. Ruthenium-catalyzed synthesis of various substituted quinolines fromα-2-nitroaryl alcohols and alcohols. References 1 (a) Gunanathan, C.; Milstein, D. Science 2013, 341, 249; (b) Michlik, S.; R. Kempe. at. Chem. 2013, 5, 140. (c) Michlik, S.; Kempe, R. Angew. Chem. Int. Ed. 2013, 52, (a) Guillena, G.; Ramón, D. J.; Yus, M. Chem. Rev. 2010, 110, (b) Dobereiner, G. E;. Crabtree, R. H. Chem. Rev. 2010, 110, 681. (c) Guillena, G.; Ramón, D. J.; Yus, M. Chem. Rev. 2009, 110, R 1 R 3 303

304 P193 SYTHESIS F GLYCLURYL ITR DERIVATIVES I LIQUID R SUPERCRITICAL CARB DIXIDE M.. Zharkov, I.V. Kuchurov, I.V. Fomenkov, S.G. Zlotin. D. Zelinsky Institute of rganic Chemistry, Laboratory of Fine rganic Synthesis, Moscow, Russian Federation Dinitroglycoluryl (DIGU) is a high-energy (VD ~ 7580 m/s, d = 1,99 g/cm 3 ), termally (deflagration temp. = С) and hydrolytically stable explosive that is used in low-sensitive molding compositions with TT as a substitute for the RDX. Commonly, it is synthesized by a nitration of the glycoluryl and its derivatives with nitric acid, acetyl nitrate or mixed acids at С under neat conditions where the temperature control is complicated and explosion risks are high. Herein, we report an alternative procedure for the synthesis of glycoluryl nitro derivatives by performing the nitration of - or C-alkylglycoluryls with the dinitrogen pentoxide in liquid or supercritical (sc) carbon dioxide. Dinitrogen pentoxide ( 2 5 ) is an active nitrating agent, which generates recoverable nitric acid as the only acidic by-product. Furthermore, carbon dioxide, being an available, non-toxic, incombustible, and thermally stable compound with a high heat capacity in liquid or supercritical state, is a highly suitable medium for nitration reactions. 1 Under proposed conditions, dinitroglycoluryl derivatives 2a-c and 4 have been prepared in 56 89% yield. H 3 C H 3 C H H R H H R 2 R H R H 2 1a-c 2 5 2a-c (56-89%) C 2, bar 5-45 o C H 3 C 3 H 2 H H 3 C 2 1, 2: R = H (a), CH 3 (b); R 2 -R 2 4 (73%) = -(CH 2 ) 4 - (c) The proposed nitration mode significantly reduces explosion risks due to the dilution of reaction mixture with liquid C 2 resistant to the action of nitrating agents. Furthermore, it eliminates the use of mixed acids that are associated with energy-consuming waste disposal and environment pollution problems. 2 The work was financially supported by the Presidium of Russian Academy of Sciences (Basic Research Program o. 8) and the Russian Foundation of Basic Research (project ). [1] I.V. Kuchurov, I.V. Fomenkov, S.G. Zlotin, V.A. Tartakovsky, Mendeleev Commun., 2013, 23, [2] I.V. Kuchurov, I.V. Fomenkov, S.G. Zlotin, V.A. Tartakovsky, Mendeleev Commun., 2014, submitted. 304

305 P194 REACTI F AMIDXIMES WITH ITRILES AT HIGH PRESSURES E.R. Kofanov 1, S.V. Baikov 1, A.A. Zharov 2, G.A. Stashina 2, I.V. Zavarzin Yaroslavl State Technical University, Laboratory for Chemistry of Steroid Compounds, Yaroslavl, Russia 2 -. D. Zelinsky Institute of rganic Chemistry, Laboratory for Chemistry of Steroid Compounds, Moscow, Russia The reaction of nitriles with amidoximes affording 1,2,4-oxadiazoles under rigid conditions (at 180 о С) in low yields has first been described in Later it was shown that the yield can be increased and the temperature of the process can be decreased by using the catalyst, namely, the ZnCl 2 /HCl system 2,3 We assumed that the reaction of amidoximes with nitriles carried out under fairly high pressure would allow one to decrease temperature and to reject the use of any catalysts and additional reagents. The reaction of amidoximes (I, R=H, -CH 3, - 2 ) with acetonitrile was studied under a pressure of 10 Kbar. An acetonitrile excess was used as a solvent. The yield of the corresponding 1,2,4-oxadiazoles (II, R=H, -CH 3, - 2 ) depends on the temperature, being 40-80% (Scheme 1). H 10 Kbar R R H CH 2 3 C I II CH 3 In addition to 1,2,4-oxadiazoles II, the formation of the corresponding substituted 3,5-diphenyl- 1,2,4-oxadiazoles (III, R=H, -CH 3, - 2 ) and 1,3,5-trimethyltriazine (IV) was detected in all cases. However, the yields of these products were insignificant. H 3 C C H 3 R R III The Barostat type setup that makes it possible to carry out investigations at pressures below 15 Kbar was used in the work 4. References 1. Weddige A, J. prakt. Chem. [2], 9, 132 (1874). 2. Yarovenko V.., Taralashvili V.K., Krayuskin M.M., and Zavarzin I.V., Tetrahedron, 1990, Vol. 40, o. 11, Yarovenko V.., Shirinyan V.Z., Ugrak B.I., Krayuskin M.M., and Zavarzin I.V., Russ. Chem. Bull., 1994, 43, Moskvin D.I and Zharov A.A., in Preparative rganic Syntheses (Collection of Works), Vol. 1. Moscow, 2006 (in Russian). C H 3 IV 305

306 P195 CVEIET DMI SYTHESIS F PLYFUSED HETERCYCLIC CMPUDS FRM SIMPLE STARTIG MATERIALS A.A. Zubarev,.A. Larionova, L.A. Rodinovskaya, A.M. Shestopalov. D. Zelinsky institute of organic chemistry, Leninsky prospekt, 47, Moscow, Russia Previously we have developed a convenient method for the synthesis of thieno[3,2-b]pyridines from malonitrile (1), carbon disulfide (2) and ethyl 4-chloroacetoacetate (4) 1. The key step of this reaction is to generate a solution of dipotassium 2,2-dicyanoetendithiolat (3), followed by its selective monoalkylation. The selectivity has been achieved by using the Ruggli-Ziegler dilution principle. Based on this approach, we have developed a convenient one-pot method for the synthesis of new condensed heterocyclic systems, thieno[3',2' : 4,5]thieno[3,2-b]pyridins and pyrimidins (6). The two consecutive domino reactions: type of the S 2 reaction the Thorpe- Ziegler reaction the Thorpe-Guareschi reaction, with the formation of thienopyridine system (5) and then type of the S 2 reaction the Thorpe-Ziegler reaction with second thiophene ring closure for this method of synthesis have been used. By using the Ruggli-Ziegler dilution principle, we have reversed order of construction of the heterocyclic system: first thiophene ring (7), and then thienopyridine system have been formed (Shceme 1.) Intermediate 7 is a convenient substrate for the synthesis of 2,5-unsymmetrically substituted thienothiophens 8. By using in this synthesis of 2-bromo-(3`,4`,5`-trimethoxy)acetophenone, we have obtained thienothiophens 9 - the first example of biheterocyclic analogues of natural anticancer agent phenstatin. Based on thienothienopyridins 6 (X = CH), were have synthesized of 2- amino-3-cyanopyrans 10, by using of domino reaction type of the Knoevenagel reaction the Michael reaction the hetero-thorpe-zieglerreaction. 1. A. M. Shestopalov, L. A. Rodinovskaya, A. A. Shestopalov., J. Comb. Chem., 2010, 12,

307 P196 DIMETHYL ETHER - ALTERATIVE MTR FUEL F.A. Babayeva, R.Q. Ahmedova, X.D. Ibragimov ational Academy of Sciences of Azerbaijan The Y.H. Mamedaliyev Institute of Petrochemical Processes The important problem of the present is the alternative energy carrier searching. This is related not only to oil stock deficit but also to ecology problems. Dimethyl ether is one of the perspective energy sources by ecological viewpoint. The perspectives of using DME as ecologically clean motor fuel alternative to oil and also ability of transportation into low-molecular olefins C2-C4 and the components of high-grade petrol attracted an interest of petrochemical scientists. Properties of DME and presence it in oxygen atom composition provides the excellent cold start of motor and abatement of noise. The main priority of DME as diesel fuel is ecologically clean expulsion. Content of toxic components in it lack of carbon-black, decreasing the substance of nitric oxide meet the ecological requirements of European standards. We carried out researches focused on DME production from methanol, designed the conditions of selective involvement of DME into the production process of low-molecular olefins C2-C4 and ¹ and atmospheric pressure. It was investigated the influence of temperature and weight hour space velocity to product yield and process selectivity. Reaction products were analyzed on gas chromatograph Auto System XL by Perkin Elmer, in the capacity of fixed phase there were used 5% methyl polyphenile siloxane. Synthesized nanostructured catalyst Zn (5%) Al 2 3 displays high activity in process of conversion methanol into DME. n initial period of process, on first 20 minutes occurs the activation of catalyst. Increasing of catalyst activation at the process of degidratational dimerisation of methanol to DME connected to brendsted acidity changes of test specimen. Activity of catalyst doesn t fall during the experiment, DME yield reaches 98.42% at selectivity 99.4%. It should be noted that the availability of using carbon dioxide for DME synthesis as potential carbon source with simultaneous utilization of current greenhouse gas also is the effective problem solving of environment and production development of DME is quite actual. 307

308 P197 TRADITIAL APPRACHES AD PERSPERTIVE IDEAS F THERMDYAMIC AALYSES F RGAIC: CHALLEGES AD ISIGHT A.K. Baev G.A.Krestov Institute of Solution Chemistry of the RAS, Ivanovo Reflection of changing in structure of liquids, solutions on enthalpies and entropies of evaporation provides possibility to perceive the peculiarities of intermolecular interactions and evaluate their energies. But organic and elementorganic compounds with alkyl ligands are in oblivion on the following reasons [1]: it was created notion historically that intermolecular interactions in solutions of this compounds are non-specific ones; comprehensive model sp3-hybridization of electron configuration of carbon atom was not exposed to doubt. At this lecture we are discussed a contradiction between thermodynamic properties of evaporation process of organic and elementorganic compounds of main groups elements obtained experimentally and predicted by above-mentioned model and substantiated the following regularities: -substantiated refusal from sp3-hybridization in CH4 and molecules of elementorganic compounds with alkyl ligand; -additional orbital dative type interaction in electron structure of main group element compounds with saturated hydrocarbon ligands and their coordination derivatives; -pentacoordinated carbon atom in specific intermolecular interactions; -employment of all bond vacancies in structure of molecules; -enthalpy and entropy of evaporation are interconnected with number and energy of specific intermolecular interactions [2]. The results of quantum chemical calculations of A(CH3)n structure are the base for refusal from sp3-hybridization, which are used for conception development of reverse dative bonding between carbon atom of alkyl ligand and central atom A of complex ARn. It is also established that: -valent 2s2(C)-electron pair remains essentially localized on carbon atom even in CH4 molecule and only two of four valent electrons of atom C situated on its three valent A 2px, 2py, 2pz take part effectively in hypervalent bonding with all of four hydrogen atoms; -carbon atom of bridge CH3-group (in particular Al2(CH3)6) forms the fifth coordination with second atom A by dative mechanism using own valent electron pair and vacant orbital of central atom A. This principle correlates with the results of X-ray investigations of alkyl compound structures [3]. In the lecture we discuss different types of specific intermolecular interactions with participation of pentacoordinated carbon atom of alkyl compounds, functional solvents, hydrogen bonds of formamide, alcohols, carbonic acids and calculations of their energies. 1. Baev A.К. Journal of Coordination Chemistry V P Baev A K. General and Applied Chemistry. Minsk. Belarusia P Baev A.K., Korolkov D.V., Book of Abstract the XVth FECHEM Conference on rganometallic Chemistry. University of Zurich. Svizeland.(2003)

309 P198 CMPLEX CMBIATIS F TRASITIAL METALS WITH REDXYLIGADS - EW TYPE CATALYST I HYDRSILICATIG REACTIS F USATURATED SILICRGAIC MMERS T.M. Chigorina, A.A. Arutyunyants, E.A. Chigorina orth ssetian State University, Vladikavkaz, Russia The catalyst is one of the most important component vulcanizing systems, allowing influence upon velocity of the vulcanizing, nature of the forming net, temperature and hardening depth, as well as allowing to obtain compositions with the necessary set physical-chemical features. In observed work catalysts of the fundamentally new type were synthesized - complex compounds of the platinum group with redox-ligands, capable to monoelectronic reverse transition bensonytril-type complex compounds of platinum, palladium and rhodium. The electrochemical characters and velocity of the complex obtained interaction with a classical hydroxylate reagent hydrid-containing silans, vinilsyloxans, were studied. The compositions, basing the vinilsyloxan rubbers, hardened with the complex of platinum with redox-ligands, give the small reconstruction peaks. The smaller eduction of the hydrogen occurs at cation-radical - sylan fragmentation in comparison with the traditional catalyst (the systems based on platinum - a Spayer catalysts). It is shown for the first time that the role of the catalyst is to generate catyon-radical low-molecular sylan, the further fragmentation of which leads to throwing out of atomic hydrogen and forming the siliconium ion. The reaction hydrosylating runs by furcated chain reaction mechanism, platinum anode - an initiator of the chain reaction. The complex compounds of metal platinum group with redox-ligands - high viability, vulcanizing velocity, high dielectric parameters; low temperature hardening ( С) compositions are obtained under usage of high active catalysts synthesized. The main advantages of catalyst synthesized are its reusability; lack of mixture spontaneous heating and temperature leap important for industrial conditions. oted that new hydrosilating catalyst rhodium semiquinolate, does not cause the metallic article corrosion. The physical-mechanical and electrical features of the polymetil-vinilsyloxan composition designed under accelerated vulcanizing are following: - conditional toughness, MPA - 1,5-5,0; - relative lengthening %; - elasticity module, MPA - 1,7-2,2; - dialectical losses tangent at frequency 10 6 Hz ; - dialectical permeability at frequency 10 6 Hz - 3-3,5. The correlation between electrochemical data and rubber hardening will allow offering the scientific foundation for search of new effective, selective and sufficiently available catalyst to polyconnection reactions. The complexes synthesized so as materials designed on their fundament will find use in the electronic technology items. 309

310 P199 THE IMMBILIZED AD RECYCLE CATALYST FR ASYMMETRIC FRIEDEL-CRAFTS REACTI V.G. Desyatkin, M.V. Anokhin, I.P. Beletskaya Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia In this work we obtained BX-ligand 1, immobilized on the polymer matrix and tested catalytic active of our catalyst. As the polymer matrix, we chose commercially available Merrifield resin. The of BX-ligand 1 immobilization on the polymer matrix was performed using the «click»-reaction. After the treatment the polymer BX-ligand 2 by copper (II) triflate catalyst 3 was obtained. Polymeric catalyst 3 was used for asymmetric Friedel-Crafts reaction indoles and different Michael acceptors (arylidenemalonates, arylidenepyruvate) and methyl 3,3,3-thrifluoropyruvate. Products of reactions were obtained with high yields (up to 99%) and high enantiomeric excess (up to 99%). The catalyst 3 was recycled of several times. 310

311 P200 SYTHESIS AD IVESTIGATI F EW Zr AD Ti CMPLEXES FR LIGMERIZATI AD PLYMERIZATI F THE ETHYLEE A.A. Khanmetov, A.H. Azizov, M.J. Khamiyev, R.V. Aliyeva, A.D. Guliev The Institute of Petrochemical Processes of Azerbaijan ational Academy of Sciences In recent years Zr and Ti complexes with ligands of different phenols are of great interest in the polymerization and oligomerization of the ethylene [1-3]. In the abstract presents the results of the synthesis and investigation a new zirconium and titanium complexes which obtained by interaction of ZrCl 4 and TiCl 4 with morfolylmethyl methyl phenol, 2- piperidinylmethyl-4-methyl phenol, 2-amino benzoic acid, 2-diethylaminomethyl -4-methyl phenol and 2- {[2,6 di (isobutyl) phenyl] iminomethyl} phenol [4]. This Zirconium complexes were investigated by IQS, DSK, and SEM. The IR spectra of the synthesized compounds presented absorption bands around 2547, 2573 and 2633 sm -1, corresponding to + R 3 H ammonium group. The absorption band also contains around sm -1,which characterizes the valence vibrations of Zr- and Ti- bonds. The pictures illustrate the complex of ZrCl 4 with 2 - piperidinyl aminomethyl - 4 methylphenol (pic1.a,b), which were obtained by the scanning electron microscope. The freshly prepared complex (prior to reaction) has a well-developed structure. As seen in pic.1b. (x 500F) after the reaction the surface remains sufficiently well developed. The separate fragments of the complex closely interconnected into a single mass. The system has been very porous and it is arranged lots of pores and channels which reacting components can be placed in the pores. a)before reaction b) after reaction Picture 1. Scanning electron microscope of Zr[4 methyl 2-()-C 6 H 3 CH 2 H(CH 2 ) 5 Cl] 2 Cl 2 The melting temperature of the synthesized complexes was determined by DSC. It was found that the melting temperature of these complexes is changed within the limits C. It was established that the synthesis of the zirconium and titanium compounds with organoaluminum compound ((C 2 H 2 ) n AlCl 3 - n, where n = 3 1 at molar ratio of Zr : Al = 1 : (10 50) leads to the formation of supported ionic liquid in the complex catalytic system, which could be active in the oligomerization and polymerization of the ethylene. A scientific opinion concerning the possibility of receiving polyethylene having various molecular and thermodynamic properties has been presented and it is proved by experimental method. btained polyethylene in the presence of titanium complexes is characterized by different molecular and thermodynamic parameters. Crystallinity degree (was determined with DSK) - 42,27 72,9%, density 0,94 97 g/sm 3 ; M w =170,2 x ,5 x 10 3 ; M n =3,9 x ,7 x 10 3 ; M w / M n = 2,62-93; Тm = 126,9 141,6 0 C. 1. Vakshouri A.R., Azizov A.H., Aliyeva R.V., Kalbaliyeva E.S. Some patent developments in the field of non metallocene catalysts for ethylene(co) polymerization (review)// Azerbaijan Petrochemical and il Refining 2009,v.38,10,p Xiao-Chao Shi and Guo-Xin Jin. Titanium and Zirconium catalysts with [,] ligands; synthesis, characterization andtheir catalytic properties for olefin polymerization/rganometallics 2012, 31 pp Ke-Ming Song, Hai-Yang Gao, Feng-Shou Liu, Jin Pan, Li-Hua Guo, Shao-Bo Zai, Qing Wu/Catal. Letter/.(2009) 131: p Azerb. Pat.J (2008) Aziz A.G., Aliyev R.V., Rasulov Ch.K. et al. 311

312 P201 MDIFIED ALKYLPHELATE ADDITIVE T THE MTR IL A.K. Kazimzadeh, E.A. aghiyeva, A.A. Gadirov, R.A. Mammadova, S.I. asirova A.M.Guliyev Institute of Chemistry of Additives of Azerbaijan ational Academy of Sciences (AAS), Beyuk-Shor Str., Block 2062, AZ1029, Baku, Azerbaijan The high speed in the development of modern machinebuilding produces the inereased requirements to the quality of motor oils. ne of the perspective direcfions of the motor quality improvement is the introduction of the new efficient additives to their composition. It is known that alkylphenolate additives are widely used as detergent - dispersant additives to the motor oils. The introduction of different heteroatoms and functional groups to the composition of additives molecule expands the range of their exploiatation action. We are suggesting the method of obtaining of the new sulphurcontaining alkylphenolate additives IXP-154 and IXP-162, representing carbonated calcium salts of condensation product of dodesylphenol or mixture of dodesylphenol and alkylsalisylic acid with formaldehyde and sulphid sodium respectively. These additives technology production has a number of advantages as compared with industrial sulfhurcontaining analogues (sulphuration is conducted at C against C for industrial samples and without H 2 S secretion). The process of obtaining of IXP-154 and IXP-162 additives consists of the following stages: - condensation of dodecylphenol (mixture of dodecylphenol and alkylsalisylic acid) with formaldehyde and natriun sulphur. - neutralization of condensation products by means of Ca(H) 2 - carbonation of neutralization products - drying and centrafuqal carbonation products. IXP-154 and IXP-162 additives have alcaly number of mqKH/q. The results of the research have shown that the obtained additives are multifunctional, giving to the motor oils high anticorrosive, antioxidative, detergent properties and are better than industrial additives ОLОА-218А and VIIP-714(carbonated sulphurphenolate calcium) for anticorrosive properties. Besides, the additive IXP-162 excels additive IXP-154 in anticorrosive properties and thermal stability, that, apparently, is provided by having in the composition of the additive of carboxilate groups in combination with sulphur atom. The additive have been investigated separately and in the composition of motor oils. By using additives IXP-154 and IXP-162, and also industrial additives M-8B and M-10Г 2 have been developed which meet the requirements for these oils and don t fall behind foreign analogues of the firm shell in exploitation properties. This with the usage of IXP-154 and IXP-162 it is possible to obtain new perspective motor oils according to the simplified and ecologically harmless technology. 312

313 P202 SYTHESIS AD MR STUDY F ADAMATYL DERIVATIVES F 1,5- DIHYDRXY- AD 1,5-DIMETHYLAPHTHALEES I.V. Peterson,.M. Svirskaya, A.A. Kondrasenko, A.I. Rubaylo Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia In continuation of studying structure and reactivity of various adamantyl derivatives of dihydroxynaphthalenes with used MR spectroscopy [1], we have investigated the interaction of 1- adamantanol with 1,5-dihydroxy-(I) and 1,5-dimethylnaphthalene (II). As a result, there were prepared: 3-(1-adamantyl)- (III) and 3,7-di(1-adamantyl)-1,5-dimethylnaphthalene (IV), and 3,7- di(1-adamantyl)-1,5-dihydroxynaphthalene (V). R 4 I - R 1 =R 3 =CH 3 ; R 2 =R 4 =H II - R 1 =R 2 =H; R 2 =R 4 =H R 3 R 1 + R 2 H CF 3 CH a: (1:1) b: (1:2) R 1 R 4 III a - R 1 =R 3 =CH 3 ; R 2 =Ad; R 4 =H IV b - R 1 =R 3 =CH 3 ; R 2 =R 4 =Ad R 2 V b - R 1 =R 3 =H; R 2 =R 4 =Ad R 3 Structure elucidation of III-V compounds and a full analysis of their 1 H and 13 C ( and MHz) spectra was carried out using CSY, HSQC, HMBC on MR spectrometer «Bruker Avance III 600» (Krasnoyarsk Regional Center for collective use SB RAS). As an example of MR studies, here presented HSQC spectrum of the compound IV (CD 2 Cl 2 ). This diadamatylsubstituted compound, as well as product V, is symmetrical, whereby the chemical shifts of protons and carbons in opposite naphthalene rings are pairwise equal. In 1 H spectrum is appeared on presence in the aromatic region two doublets (δ 7.44 and 7.71 ppm) with J =1.6 Hz, which indicated about their metha-position relative to each other and thus confirms connection of the adamantyl group to position 3 and 7. Suitable cross-peaks with two signals (δ and ppm) in 13 C spectrum further confirm the symmetrical arrangement of adamantyl group in compounds IV and V. References 1. I.V. Peterson,.M. Svirskaya. A.A. Kondrasenko, A.I. Rubaylo. Magn. Reson. Chem. 2013, 51, This work was supported by Siberian branch of Russian academy of science (project of multidisciplinary integration fundamental research 18). 313

314 P203 DRAMATIC RECSTRUCTI F CBALT CATALYSTS DURIG FISCHER-TRPSCH SYTHESIS: DRIVIG FRCE AD MECHAISTIC CSEQUECES M. Saeys 1, A. Banerjee 2, K. Gunasooriya Laboratory for Chemical Technology, Ghent University, Ghent, Belgium 2 - Department of Chemical and Biomolecular Engineering, ational University of Singapore The strong adsorption of reaction intermediates can introduce massive structural changes to the surface of catalyst particles under reaction conditions [1,2] and often the catalytically active sites form only under reaction conditions. Fischer-Tropsch synthesis converts synthesis gas, a mixture of C and H 2, to long-chain hydrocarbons and water over supported cobalt catalysts. Under high C pressures, cobalt single crystals are found to undergo a massive reconstruction, leading to the spontaneous formation of sub-2-nm cobalt islands, together with the formation of defect sites as observed by DRIFT spectroscopy. [2] The driving force for this reconstruction and its kinetic consequences remain poorly understood. Using Density Functional Theory with the RPBE-VdW functional, we show that the unusual stability of square planar-carbon at the B5 step edges [3], as well as the attractive interaction between this square-planar carbon and C at the neighboring edge site lead to a negative edge creation energy under reaction conditions, driving the formation of nano-scale islands of well-defined shapes (Figure). Bonding analysis based on both Bloch states and atural Bond rbitals elucidates the electronic origin for the exceptional stability of these structures. The island sites created under reaction conditions are not fully covered during the FT reaction and the available vacancies provide active sites for rapid C activation, the initiation step in the FT reaction mechanism [4]. Model for the nano-islands formed under Fischer-Tropsch conditions. The active sites, highlighted in green, are created by the formation of the nano-islands. References [1] Tao, Dag, Wang, Liu, Butcher, Bluhm, Salmeron, Somorjai, Science, : 850 (2010); Hansen, Wagner, Helveg, Rostrup-ielsen, Clausen,Topsøe, Science, , 2053 (2002) [2] Wilson, de Groot, J. Phys. Chem., 99, 7860, (1995) [3] Alexandrova, Trinh, Saeys, submitted [4] Zhuo, Borgna, Saeys, J Catal 297, 217, (2013) 314

315 P204 UIQUE RLE F THE MULTI-LABILITY F PLYDETATE LIGADS FR PD-CATALYZED C- AD C-S CRSS CUPLIG REACTIS: EW REACTI PATHWAYS AD CATALYTIC RESTIG STATES M. Saeys 1,. Wijaya 2, J.-C. Hierso Laboratory for Chemical Technology, Ghent University, Ghent, Belgium 2-1Chemical and Pharmaceutical Engineering, Singapore-MIT Alliance, ational University of Singapore, Singapore 3 - Institut de Chimie Moleculaire, Universite de Bourgogne, Dijon, France Versatile and robust tridentate ferrocenylphosphanes exhibit remarkable potential as supporting ligands for Pd-catalyzed C- coupling reactions. [1] The air-stable Pd-triphosphane system performed efficiently for the selective heteroaryl ether synthesis for catalyst loadings as low as 0.2 mol% by opening a reaction path through an unusual penta-coordinated transition state (TS) as demonstrated by DFT calculations (Figure). atural Bond rbital analysis shows that the stability of the transition state originates from a 3-center-4-electron bond between the P lone pair, the Pd center and a low-lying acceptor orbital on the substrate. nly for constrained polyphosphane ligands, this gain in TS stability is not overwhelmed by an entropy penalty. [2] DFT calculations further indicate that a similar penta-coordinated reaction path should facilitate C-S cross-coupling reactions. [3] Unfortunately, constrained tridentate ferrocenylphosphanes perform poorly for this cross-coupling reaction. Mechanistic studies using DFT show that the stability of the catalytic resting states [4] cause this surprisingly different outcome. In C-S cross-coupling reactions, the strong Pd-S bond stabilizes the resting states and a penta-coordinated reaction path does not facilitate escape from those stable resting states. The stability of the resting states suggests that ligands with a larger bite angle, and hence faster reductive elimination, should help the catalyst system re-enter the catalytic cycle. Both theory and experiment show that a tetradentate binuclear Pd catalyst therefore displays the highest activity, offering an optimal balance between enthalpy gain and entropy penalty. Independent synthesis of the resting states for the variopus ligands also confirms the relative reactivity predicted by theory. tb u tb u F e Å P P h 2 P P h A r 2 P d II H e ta r P (i-p r) 2 R. E. tb u tb u F e Å P P h 2 P P h A r 2 P d II - H e ta r A r H e ta r P (i-p r) 2 tb u tb u F e P P h 2 P P h 2 P d 0 P ( i- P r) 2 P d (II) in te r m e d ia te T r a n s itio n s ta te P d (0 ) in te r m e d ia te C- reductive elimination through a unique penta-coordinated transition state lowers the activation free energy barrier by 10 kj/mol and increased the catalytic activity by two orders of magnitude. References [1] Platon, Cui, Mom, Richard, Saeys, Hierso, Adv. Syn. Cat., 353, 3403, [2] Wijaya, Cui, Platon, Hierso, Saeys, in preparation [3] Platon, Wijaya, Rampazi, Cui, Rousselin, Saeys, Hierso, submitted [4] Alvaro, Hartwig, J. Am. Chem. Soc., 2009, 131,

316 P205 THERETICAL AD EXPERIMETAL STUDIES PRCESSES LIGMERIZATI AD ALKYLATI C6-C12 α-lefis I THE PRESET IIC LIQUID CATALYTIC SYSTEMS Kh. H. Seidova, A.H. Azizov, R.V. Aliyeva, A.M. Abdullayeva The Institute of Petrochemical Processes of the Azerbaijan ational Academy of Sciences In recent years, ionic liquids (ILs) are of great interest in the area of oligomerization and alkylation processes. ILs have several benefits (low melting point, low volatility, reusability), including a lot of good dissolved metal complexes. These properties are perfect for two-phase catalysis. We carried out work on the oligomerization of C6-C12 α-olefins in the presence chloraluminate ionic liquids based on AlCl3 and various amine hydrochlorides (triethylamine hydrochloride, dietilamin hydrochloride, pyridine hydrochloride). In ILs were dissolved Ti-containing complexes which is prepared by reacting TiCl4 and sterically hindered aminophenоl. In the presence of these ILs catalytic systems derived oligoalkylnaphtenic oil (Mw= , Mn= , Mw/Mn =, IV= ), not requiring hydrogenation step (since they do not contain double bonds in the composition). Kinetic regularities (reaction order, activation energy, etc.) were installed on the basis of experimental and theoretical data. We have also carried out work on oligoalkylation toluene decene-1 in the presence of IL catalytic systems. btained products were analyzed using chromatograph methods IR-, MR-, UV-, and DSC. It was established that they had Mw = , Mn = , Mw / Mn = 1,17-1,3, IV = Thus, in the presence of IL catalytic systems it is possible to obtain oligoalkylaromatic and oligomeric products which can be used as synthetic lubricants for various applications. 316

317 P206 QUATUM SIMULATI F THE REACTI MECHAISM F RGACATALYSES C.H. Yu ational Tsing Hua University, Department of Chemistry, Hsinchu, Taiwan rganocatalysis has received remarkable attraction recently. For instances, organic molecules have been widely used as catalysts in the asymmetric synthesis of natural products. The reaction mechanism of many chemical reactions of this type are too complicated to be tackled efficiently by traditional optimization methods of quantum chemistry. The idea of incorporating the chemical nature of the reaction into the search algorithm results in the constrained reduced-dimensionality (CRD) algorithm. 1 The CRD algorithm constructs the search path stepwise from linear combinations of a small set of manually chosen coordinates (predictors). The rest, and majority, of the coordinates (correctors) are optimized at every step of the search path to minimize the total energy such that the search path becomes a minimum energy path connecting transition states and the desired products starting from the reactants. Dynamic constraints, which are automatically activated and later revoked depending on the state of some particular coordinates among the predictors, are quite often required to guide the search of reaction path. Practical applications of the constrained CRD algorithm to the study of stereoselective organocatalysis successfully reveal the catalytic mechanism of the phosphine and amine catalyzed reactions of the cycloaddition of allenoates and enones; and the nornicotine catalyzed Mannich reaction. The cycloaddition of allenoates and enones yields [3+2] cyclopentenes in phosphine catalysis, and [2+4] dihydropyrans or pyrans in amine catalysis. 2 The quantum calculation not only explains the different reactivity of the two types of catalysts but also reveals a new path to the α- [2+4] product via an intermediate Rauhut-Currier reaction in amine catalysis. In the latter system, the computations show that nornicotine can catalyze the intermolecular Mannich reaction in wet solvents and water. The significant catalytic effect is owing to the elimination of the bottleneck of the enol-formation step. In addition to the two examples, the constrained CRD algorithm has been applied in many other complex reactions. 1. T. Lankau, C. H. Yu, J. Chem. Phys. 138 (2013) ; doi: / G. T. Huang, T. Lankau, and C. H. Yu, J. rg. Chem., 79, , 2014; doi: /jo402609v. 317

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