Recent Advances of Alkyne Metathesis. Group Meeting Timothy Chang
|
|
- Priscilla Riley
- 5 years ago
- Views:
Transcription
1 Recent Advances of Alkyne Metathesis Group Meeting Timothy Chang
2 Fischer Carbyne and Schrock Alkylidyne Fischer Doublet LX type 4e Schrock Quartet X 3 type 6e -1-3 lone pair covalent p-back bonding Weak donor L 3 covalents Strong donor L The Organometallic Chemistry of the Transition Metals, 4 th Ed., Crabtree. Organotransition Metal Chemistry, From Bonding to Catalysis, Hartwig.
3 Carbyne Complexes, Fischer et. al. 1988, VCH Group Orbitals of + CR Fragment
4 Carbyne Complexes, Fischer et. al. 1988, VCH MOs of Fischer Carbyne
5 Group Orbitals of L 3 M - Fragment Encyclopedia of Inorganic Chemistry, Electronic Structure of Organometallic Compounds, Albright, T. A.
6 Carbyne Complexes, Fischer et. al. 1988, VCH Molecular Orbitals of L 3 M(CR)
7 A Brief History of Alkyne Metathesis Pennellar, F.; Banks, R. L.; Bailey, G. C. J. Chem. Soc., Chem. Commun. 1968, Mortreux, A.; Blanchard, M. J. Chem. Soc., Chem. Commun. 1974, 786. Katz, T. J.; McGinnis, J. J. Am. Chem. Soc. 1975, 97, For an account, see Schrock, R. R. Polyhedron, 1995, 14, 3177.
8 Catalyst Deactivation by Dimerization and Ring Expansion Zhang, W.; Moore, J. S. Adv. Synth. Catal. 2007, 349, 93.
9 Zhang, W.; Moore, J. S. Adv. Synth. Catal. 2007, 349, 93. Pseudopoisoning Effect
10 Schrock et. al. J. Am. Chem. Soc. 1981, 103, Zhang, W.; Moore, J. S. Adv. Synth. Catal. 2007, 349, 93. Preparation of (Me 3 CO) 3 W(CCMe 3 )
11 Application to RCAM Thioether, basic nitrogen containing functional groups are not compatible. Tolerate acidic proton of a secondary amide. Fürstner et. al. Angew. Chem. Int. Ed. 1998, 37, 1734 and J. Am. Chem. Soc. 1999, 121,
12 Curious Effect of Halogenated Solvents Secondary amide is not tolerated. Fürstner et. al. Chem. Eur. J. 2001, 7, 5299 and J. Am. Chem. Soc. 1999, 121, 9453
13 Major Components of the Molybdenum Species Ar = 3,5-xylyl 1 : 2 not active Why is 3 not catalytically active? Why are terminal alkynes not viable substrates? Deprotiometallacyclobutadiene Schrock et. al. J. Am. Chem. Soc. 1985, 107, 5987 Polyhedron 1995, 15, 3177
14 Cross Metathesis 1 Fürstner, A., Mathes, C. Org. Lett. 2001, 3, 221
15 Cross Metathesis 1 Fürstner, A., Mathes, C. Org. Lett. 2001, 3, 221
16 Application of RCM and RCAM to Macrocyclization RCM Schinzer et. al. ACIEE 1997, 36, 523. RCAM Fürstner et. al. Chem. Eur. J. 2003, 7, 5299.
17 Reductive Recycle Strategy for Catalyst Preparation Ar = 3,5-xylyl - Active catalyst is generated in the presence of various phenols. - Electron-deficient ligands make the catalysts more active e.g. p-nitrophenol (low cost) - Catalyst is active in MeCN even though it is a coordinating solvent. - Secondary amide and thiophene containing molecules can be used. - Bulky ligand is not required. Apparently electronic factor dominates. - Bulky ligands slows down both dimerization and metathesis presumably. Moore et. al. Org. Syn. 2007, 84, 163.
18 Effects of Alkyl Substituent and Ligand R = Et 5 Ar = 3,5-xylyl Optimal R = Et Optimal Ligand = p-nitrophenol (cheaper) R = Me gives polybutyne Equilibrium ratio of 13:14 = 2:3 (established from both 13 and 14, respectively) Moore et. al. J. Am. Chem. Soc. 2004, 126, 329.
19 Homodimerization Substrate Scope R = Et 5 Ar = 3,5-xylyl a Closed system, d8-toluene, 20 C, t1/2 is the time required for the reaction to reach 50% of final constant ratio of 10 to 12. b Open driven condition, solvent 1,2,4-trichlorobenzene, 30 C, 22 h, 1 mm Hg, yield based on isolated product. c Ligand A ) R,R,R-trifluoro-o-cresol. d Ligand B ) p-nitrophenol.
20 Solvent Effect and Precipitation Strategy R = Et 5 Ar = 3,5-xylyl Conversion CHCl 3, Toluene: 100% (0.5 h) CH 3 CN, THF: 76% (8 h) Acetone: 40% (catalyst decomposition) DMF, MeOH: 0% Precipitation strategy can be utilized to drive the equilibrium towards desired product such as 7. Aprotic, non-coordinating solvents are preferred. Moore et. al. J. Am. Chem. Soc. 2004, 126, 329.
21 Preparation of Shape-Persistent Macrocycles by PPT Strategy Zhang, W.; Moore, J. S. J. Am. Chem. Soc. 2004, 126,
22 Catalyst Prepared from Nitrides by Metathesis with Alkynes One major reason that MeCN cannot be used Schrock, Organometallics 1986, 5, 398. Johnson et. al. J. Am. Chem. Soc. 2006, 128, Johnson et. al. Inorg. Chem. 2005, 44, and 38 are preferred thermodynamically. - The formation of 38 is irreversible. - Idea: in situ generation of catalyst by metal nitride/metal alkylidyne interconversion Zhang, W.; Moore, J. S. Adv. Synth. Catal. 2007, 349, 93.
23 Development Towards a Robust and Practical Precatalyst distorted square pyramidal Fürstner et. al. J. Am. Chem. Soc. 2009, 131, 9468.
24 Scope 11 can be weighed in air and used under dry air (need increased loading) Incompatible: epoxide, aldehyde, acyl chloride Fürstner et. al. J. Am. Chem. Soc. 2009, 131, 9468
25 Improvements on Triphenylsilanolate Bound Mo (Pre)Catalyst Typical Reaction Conditions for Homodimerization, CM, RCAM (A) 15 (10 mol %), MnCl 2 (10 mol %), MS 5 Å, toluene, 80 C, 30 min, then addition of the substrate and reaction at 80 C or 100 C (for CM). (B) 24 (2 mol %), toluene, ambient temperature, MS 5 Å. (C) 25 (5 mol %), MnCl 2 (5 mol %), toluene, 80 C, 30 min; then addition of the substrate and MS 5 Å, and reaction at ambient temperature. 15 is stable on bench top for storage. Fürstner et. al. J. Am. Chem. Soc. 2010, 132,
26 Scope Incompatible with aldehyde. Previous stoichiometric experiment showed its conversion to nitrile. Fürstner et. al. J. Am. Chem. Soc. 2010, 132,
27 Roles of Molecular Sieve MS removes butyne MS helps liberate Et 2 O Fürstner et. al. J. Am. Chem. Soc. 2010, 132, Å MS has no sig. effect (i.e. not equilibrium effect of H 2 O)
28 Probing the Active Mo Species trace Hypotheses: The small amounts of alkylidynes, such as 16, formed in the mixture must be superbly active 12. L acts as a reservoir (slow release) (still show catalytic activity at 80 o C for days) The hypotheses were tested using 19 and 24. Fürstner et. al. J. Am. Chem. Soc. 2010, 132,
29 Preparation of Molybdenum Alkylidyne Complexes Fürstner et. al. J. Am. Chem. Soc. 2010, 132,
30 An Extraordinary Active Metathesis Catalyst Equilibrium reached at ~ 25 min Fürstner et. al. J. Am. Chem. Soc. 2010, 132,
31 Application of RCAM to the Synthesis of Lactimidomycin Lactimidomycin Seven sp 2 C in a 12-membered lactone Key steps: Ring closing alkyne metathesis and trans-hydrosilylation 1.2 g scale 84% Fürstner et. al. J. Am. Chem. Soc. 2010, 132,
32 Imidazolin-2-iminato Tungsten Catalyst hexane (4.5 mm) 2 h, 95% Tamm et. al. Angew. Chem. Int. Ed. 2007, 46, 8890.
33 Conclusion - New (pre)catalysts are much more functional group tolerant and efficient. - Bench top stable pre-catalyst has emerged (silanolate bound Mo complexes). - The yields of cross-metathesis are generally moderate. - RCAM and homodimerization are relatively mature. - Three ways to drive the equilibrium of metathesis: (1) reduced pressure, (2) precipitation and (3) molecular sieve - Mechanism of some pre-catalysts is still unknown (tris-amido Mo complex). - Promising in the area of ADIMET and Shape Persistent Macromolecules. For reviews on: Alkyne Metathesis, see Zhang, Moore Adv. Synth. Catal. 2007, 349, 93. RCAM, see Fürstner, Davies Chem. Commun. 2005, Carbyne Complexes, Fischer et. al. 1988, VCH Verlagsgesellschaft Handbook of Metathesis: Catalyst Development, Grubbs, Ch 1.11
Alkyne metathesis by molybdenum and tungsten alkylidyne complexes
Alkyne metathesis by molybdenum and tungsten alkylidyne complexes The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation As Published
More informationNew perspectives in metal-catalyzed metathesis: Alkyne and Z-selective olefin metathesis, new powerful tools for total synthesis
New perspectives in metal-catalyzed metathesis: Alkyne and Z-selective olefin metathesis, new powerful tools for total synthesis Ophélie Quinonero Literature - Group Meeting 31/03/2014 1 Introduction Metathesis:
More informationScission of Dinitrogen by a Molybdenum(III) Xylidene Complex. CHM 5.33 Fall 2005
Scission of Dinitrogen by a Molybdenum(III) Xylidene Complex CHM 5.33 Fall 2005 Introduction The experiment is based on research performed in the laboratory of Professor Cummins during the early 90 s.
More informationEnantioselective Borylations. David Kornfilt Denmark Group Meeting Sept. 14 th 2010
Enantioselective Borylations David Kornfilt Denmark Group Meeting Sept. 14 th 2010 30.000-foot View Enantioenriched Organoboranes What to do with them Crudden C. M. et. al., Eur. J. Org. Chem. 2003, 46
More informationWe herein report the use of bidentate, chelating
pubs.acs.org/macromolecules Bidentate Phenoxides as Ideal Activating Ligands for Living Ring- Opening Alkyne Metathesis Polymerization Danielle F. Sedbrook, Daniel W. Paley, Michael L. Steigerwald, Colin
More informationIron Catalysed Coupling Reactions
LONG LITERATURE REPORT Iron Catalysed Coupling Reactions Mingyu Liu 2017. 8. 31 1 Fe [Ar]3d 6 4s 2 The fourth most common element in the Earth s crust Relatively less understanding and manipulation of
More informationN-Heterocyclic Carbenes (NHCs)
N-Heterocyclic Carbenes (NHCs) In contrast to Fischer and Schrock type carbenes NHCs are extremely stable, inert ligands when complexed to a metal centre. Similar to phosphine ligands they are electronically
More informationDeactivation Pathways in Transition Metal Catalysis
Deactivation Pathways in Transition tal Catalysis Why Study Catalyst Decomposition? decomposition active for catalysis inactive for catalysis "One of the reasons for [the] limited understanding [of catalyst
More informationLecture 6: Transition-Metal Catalysed C-C Bond Formation
Lecture 6: Transition-Metal Catalysed C-C Bond Formation (a) Asymmetric allylic substitution 1 u - d u (b) Asymmetric eck reaction 2 3 Ar- d (0) Ar 2 3 (c) Asymmetric olefin metathesis alladium π-allyl
More informationOlefin Metathesis ROMP. L n Ru= ROMP n RCM. dilute
lefin Metathesis MP: ing-opening metathesis polymerization Thermodynamically favored for 3,4, 8, larger ring systems Bridging groups (bicyclic olefins) make ΔG polymerization more favorable as a result
More informationThe aza-baylis-hillman Reaction: Mechanism, Asymmetric Catalysis, & Abnormal Adducts. Larry Wolf SED Group Meeting
The aza-baylis-hillman Reaction: Mechanism, Asymmetric Catalysis, & Abnormal Adducts Larry Wolf SED Group Meeting 04-10-07 Outline Brief historical account and Utility Mechanism Different methods for asymmetric
More informationdeactivation or decomposition is therefore quantified using the turnover number.
A catalyst may be defined by two important criteria related to its stability and efficiency. Name both of these criteria and describe how they are defined with respect to stability or efficiency. A catalyst
More informationN-Heterocyclic Carbenes (NHCs)
N-Heterocyclic Carbenes (NHCs) In contrast to Fischer and Schrock type carbenes NHCs are extremely stable, inert ligands when complexed to a metal centre. Similar to phosphine ligands they are electronically
More informationAnti-Markovnikov Olefin Functionalization
Anti-Markovnikov Olefin Functionalization ~Prof. Robert H. Grubbs Work~ 4 th Literature Seminar July 5, 2014 Soichi Ito (D1) Contents 1. Introduction Flow of Prof. Grubbs Research Markovnikov s Rule Wacker
More informationsp 3 C-H Alkylation with Olefins Yan Xu Dec. 3, 2014
sp 3 C-H Alkylation with Olefins, Yan Xu Dec. 3, 2014 1) sp 3 C-H Alkylation via Directed C-H activation 2) Hydroaminoalkylation (still via C-H activation) 3) Hydrohydroxyalkylation (via radical chemistry)
More informationCarbenes and Olefin Metathesis
arbenes and Olefin etathesis Peter H.. Budzelaar etal-carbon multiple bonds any transition metals form not only - single bonds but also = and (more rare) even bonds. omplexes containing an = bond are called
More informationRecent Advances in C-B Bond Formation through a Free Radical Pathway
Recent Advances in C-B Bond Formation through a Free Radical Pathway G. Yan. D. Huang, X. Wu, Adv. Synth. Catal. 2017, 359, 188. Daniel Meyer University of Bern 18.01.2018, Topic Review Classical Methodes
More informationN-HETEROCYCLIC CARBENES: STRUCTURE AND PROPERTIES
N-HETEROCYCLIC CARBENES: STRUCTURE AND PROPERTIES Zachery Matesich 24 February 2015 Roadmap 2 Introduction Synthetic Methods History of NHCs Properties of NHCs Nature of the carbene Structural properties
More informationAsymmetric Synthesis of Medium-Sized Rings by Intramolecular Au(I)-Catalyzed Cyclopropanation
Asymmetric Synthesis of Medium-Sized ings by Intramolecular Au(I)-Catalyzed Cyclopropanation 1 2 Iain D. G. Watson, Stefanie itter, and F. Dean Toste JACS, ASAP, 1/22/2009 DI: 10.1021/ja8085005 2.5 mol%
More informationTransition Metal-Catalyzed Carbon-Carbon Bond Cleavage (C-C Activation) Group Meeting Timothy Chang
Transition Metal-Catalyzed Carbon-Carbon Bond Cleavage (C-C Activation) Group Meeting 01-15-2008 Timothy Chang Outlines - Fundamental considerations, C-H versus C-C activation - Orbital interactions -
More informationHighly Efficient, Convergent, and Enantioselective Synthesis of Phthioceranic Acid
Highly Efficient, Convergent, and Enantioselective Synthesis of Phthioceranic Acid Shiqing Xu, Akimichi Oda, Thomas Bobinski, Haijun Li, Yohei Matsueda, and Ei-ichi Negishi Angew. Chem. Int. Ed. 2015,
More informationDevelopment, Application and Understanding of Synthetic Tools!
Homogene Katalyse Wie kann man schneller, effizienter und umweltfreundlicher organische Moleküle und Polymere synthetisieren? Wie funktionieren diese Synthesewerkzeuge? Prof. Dr., Organometallic Chemistry,
More informationCopper-Catalyzed Reaction of Alkyl Halides with Cyclopentadienylmagnesium Reagent
Copper-Catalyzed eaction of Alkyl Halides with Cyclopentadienylmagnesium eagent Mg 1) cat. Cu(Tf) 2 i Pr 2, 25 o C, 3 h 2) H 2, Pt 2 Masahiro Sai, Hidenori Someya, Hideki Yorimitsu, and Koichiro shima
More informationOrganic Chemistry Laboratory Summer Lecture 6 Transition metal organometallic chemistry and catalysis July
344 Organic Chemistry Laboratory Summer 2013 Lecture 6 Transition metal organometallic chemistry and catalysis July 30 2013 Summary of Grignard lecture Organometallic chemistry - the chemistry of compounds
More informationMichelangelo Gruttadauria
Michelangelo Gruttadauria Dipartimento di Scienze e Tecnologie Biologiche, Chimiche e Farmaceutiche, Università di Palermo, Viale delle Scienze - Edificio 17, 90128, Palermo 1 Main focus theme: Organic
More informationSynthesis of coumarins by ring-closing metathesis*
Pure Appl. Chem., Vol. 75, No. 4, pp. 421 425, 2003. 2003 IUPAC Synthesis of coumarins by ring-closing metathesis* Arnab K. Chatterjee, F. Dean Toste, Steven D. Goldberg, and Robert H. Grubbs Arnold and
More informationC H Activated Trifluoromethylation
Literature report C H Activated Trifluoromethylation Reporter:Yan Fang Superior:Prof. Yong Huang Jun. 17 th 2013 Contents Background Trifluoromethylation of sp-hybridized C-H Bonds Trifluoromethylation
More informationTautomerism and Keto Enol Equilibrium
Tautomerism and Keto Enol Equilibrium Enols & enolates are important nucleophiles in organic & biochemistry. Keto-Enol Equilibrium: Tautomerisation can be catalyzed by either acids or bases. Relative stability
More informationLigand Effects in Nickel Catalysis. Anthony S. Grillo Chem 535 Seminar October 22, 2012
Ligand in Nickel Catalysis Anthony S. Grillo Chem 535 Seminar October 22, 2012 Transition Metals in Chemistry Organotransition Metal Chemistry, Hartwig, J. F. University Science Books: Mill Valley, CA,
More informationCHEM 251 (4 credits): Description
CHEM 251 (4 credits): Intermediate Reactions of Nucleophiles and Electrophiles (Reactivity 2) Description: An understanding of chemical reactivity, initiated in Reactivity 1, is further developed based
More informationsp 3 C-H insertion by α-oxo Gold Carbene B4 Kei Ito
1 sp 3 C-H insertion by α-oxo Gold Carbene B4 Kei Ito 2016. 1. 30 1. Introduction 2 About Carbene 3 Brief history of carbene (~2000) Carbene Neutral compounds featuring a divalent carbon atom with only
More informationCatellani Reaction (Pd-Catalyzed Sequential Reaction) Todd Luo
Catellani Reaction (Pd-Catalyzed Sequential Reaction) Todd Luo 2014.1.6 1 Content Introduction Progress of Catellani Reaction o-alkylation and Applications o-arylation and Applications Conclusion and Outlook
More informationSteric and Electronic Controllers in Ring-Closing Metathesis Reactions. Jennifer E. Farrugia October 29, 2003
Steric and Electronic Controllers in Ring-Closing Metathesis Reactions Jennifer E. Farrugia October 29, 2003 Steric and Electronic Controllers How do substrate sterics affect the reactivity/ selectivity
More informationOCR (A) Chemistry A-level. Module 6: Organic Chemistry and Analysis
OCR (A) Chemistry A-level Module 6: Organic Chemistry and Analysis Organic Synthesis Notes by Adam Robertson DEFINITIONS Heterolytic fission: The breaking of a covalent bond when one of the bonded atoms
More informationThe Mechanism of Rhenium Catalyzed Olefination of Aldehydes. Nathan Werner Denmark Group Meeting July 22 nd, 2008
The Mechanism of Rhenium Catalyzed Olefination of Aldehydes Nathan Werner Denmark Group Meeting July 22 nd, 2008 Introduction First Use of Phosphanes to Olefinate Carbonyls: oxaphosphetane Advantages:
More informationMetal Hydrides, Alkyls, Aryls, and their Reactions
Metal Hydrides, Alkyls, Aryls, and their Reactions A Primer on MO Theory σ-bonding in Organotransition Metal Complexes M-C Bond Energies in Organotransition Metal Complexes Thermodynamic Predictions
More informationUse of Cp 2 TiCl in Synthesis
Use of 2 TiCl in Synthesis eagent Control of adical eactions Jeff Kallemeyn May 21, 2002 eactions of 2 TiCl 1. Pinacol Coupling H H H 2. Epoxide pening H H E H Chemoselectivity Activated aldehydes (aromatic,
More informationChem Selected Aspects of Main Group Chemistry
Selected Aspects of Main Group Chemistry For the rest of the course, we will look at some aspects of the chemistry of main group compounds. The basic principles that you have learned concerning atoms,
More informationCarbenes and Carbene Complexes I Introduction
Carbenes and Carbene Complexes I Introduction A very interesting (honest) class of radical-like molecules Steadily becoming more important as they find far more synthetic applications We will primarily
More informationAsymmetric Palladium Catalyzed Cross-Coupling Reactions. Topic Talk September 4 th, 2014 Morken Lab Emma Edelstein 1
Asymmetric Palladium Catalyzed Cross-Coupling Reactions Topic Talk September 4 th, 2014 Morken Lab Emma Edelstein 1 Palladium Catalyzed Cross-Coupling Reactions 2 Kumada/Negishi Cross-Coupling Kumada:
More informationDirect Catalytic Cross-Coupling of Organolithium
Literature report Direct Catalytic Cross-Coupling of Organolithium Compounds Reporter: Zhang-Pei Chen Checker: Mu-Wang Chen Date: 02/07/2013 Feringa, B.L.et al. Feringa, B. L. et al. Nature Chem. 2013,
More informationAnswers to Assignment #5
Answers to Assignment #5 A. 9 8 l 2 5 DBE (benzene + 1 DBE) ( 9 2(9)+2-9 8+1+1 = 10 ˆ 5 DBE) nmr pattern of two doublets of equal integration at δ7.4 and 7.9 ppm means the group (the δ7.9 shift) IR band
More informationThe Mechanism of Pd-Catalyzed Amination Controversy.. And Conclusion?
The chanism of d-catalyzed Amination Controversy.. And Conclusion? R H R1 R 2 d(dba) 2 BIA, h R R1 R 2 Steve Tymonko SED Group eting 5/9/06 d-catalyzed Amination- Tin Initial Report- Kosugi, 1983 n-bu
More informationChem 263 Notes March 2, 2006
Chem 263 Notes March 2, 2006 Average for the midterm is 102.5 / 150 (approx. 68%). Preparation of Aldehydes and Ketones There are several methods to prepare aldehydes and ketones. We will only deal with
More informationMultiple Metal-Carbon Bonds for Catalytic Metathesis Reactions. Nobel Lecture December 8, 2005
Multiple tal-arbon Bonds for atalytic tathesis eactions obel Lecture December 8, 2005 1 tal-carbon double and triple bonds in which the transition metal is in a "low oxidation state" were discovered by
More informationA Simple Introduction of the Mizoroki-Heck Reaction
A Simple Introduction of the Mizoroki-Heck Reaction Reporter: Supervisor: Zhe Niu Prof. Yang Prof. Chen Prof. Tang 2016/2/3 Content Introduction Intermolecular Mizoroki-Heck Reaction Intramolecular Mizoroki-Heck
More informationRecent applications of chiral binaphtholderived phosphoric acid in catalytic asymmetric reactions
Recent applications of chiral binaphtholderived phosphoric acid in catalytic asymmetric reactions 1. Seayad, J.; Seayad, A. M.; List, B. J. Am. Chem. Soc. 2006, ASAP. 2. Storer, R. L.; Carrera, D. E.;
More informationMolybdenum-Catalyzed Asymmetric Allylic Alkylation
Molybdenum-Catalyzed Asymmetric Allylic Alkylation X MoL n u u * Tommy Bui 9/14/04 Asymmetric Allylic Alkylation from a Synthetic Viewpoint X X M u u * and/or u form a C-C bond with the creation of a new
More informationBio-inspired C-H functionalization by metal-oxo complexes
1 Literature Seminar Bio-inspired C-H functionalization by metal-oxo complexes 2016. 7. 23. Nagashima Nozomu 2 C-H functionalization by enzymes Enzymes enable aliphatic C-H functionalization 3 P450 oxidation
More informationRachel Whittaker Dong Group Literature Talk October 10, Ref: Perez-Temprano, M.H, Casares, J.A., Espinet, P., Chem. Eur. J. 2012, 18, 1864.
Rachel Whittaker Dong Group Literature Talk October 10, 2013 Ref: Perez-Temprano, M.H, Casares, J.A., Espinet, P., Chem. Eur. J. 2012, 18, 1864. Overview Introduction Group Exchange C-C Bond Forming Reactions
More informationPlanar-Chiral Phosphine-Olefin Ligands Exploiting a (Cyclopentadienyl)manganese(I) Scaffold to Achieve High Robustness and High Enantioselectivity
Planar-Chiral Phosphine-Olefin Ligands Exploiting a (Cyclopentadienyl)manganese(I) Scaffold to Achieve High Robustness and High Enantioselectivity Reporter: Cong Liu Checker: Hong-Qiang Shen Date: 2017/02/27
More informationπ-alkyne metal complex and vinylidene metal complex in organic synthesis
Literature Seminar 080220 Kenzo YAMATSUGU (D1) π-alkyne metal complex and vinylidene metal complex in organic synthesis 0. Introduction ' ' = π-alkyne metal complex vinylidene metal complex ecently, electrophilic
More informationMn Reagent & Organomanganese: Neglected Powerful Tool. Reporter: Li Zhuo Advisor: Prof. Yang Prof. Chen Prof. Tang
Mn Reagent & Organomanganese: Neglected Powerful Tool Reporter: Li Zhuo Advisor: Prof. Yang Prof. Chen Prof. Tang 1 Content Introduction Oxidation by Mn(VII) & Mn(IV) Epoxidation & Cyclopropanation Radical
More informationSynthesis of Polyfluorinated and Polychlorinated Hydrocarbons
Synthesis of Polyfluorinated and Polychlorinated Hydrocarbons Yong Guan Feb. 13, 2009 Nicoletti, M.; O Hagan, D.; Slawin, A.M.Z. J. Am. Chem. Soc. 2005, 127, 482. Hunter, L.; O Hagan, D.; Slawin, A.M.Z.
More informationChiral Supramolecular Catalyst for Asymmetric Reaction
Chiral Supramolecular Catalyst for Asymmetric Reaction 2017/1/21 (Sat.) Literature Seminar Taiki Fujita (B4) 1 Introduction Rational design of chiral ligands remains very difficult. Conventional chiral
More informationA. Loupy, B.Tchoubar. Salt Effects in Organic and Organometallic Chemistry
A. Loupy, B.Tchoubar Salt Effects in Organic and Organometallic Chemistry 1 Introduction - Classification of Specific Salt Effects 1 1.1 Specific Salt Effects Involving the Salt's Lewis Acid or Base Character
More informationummary Manipulating Radicals
Manipulating Radicals ummary Modern catalysis research tries to address issues such as material scarcity, sustainability or process costs. One solution is to replace expensive and scarce noble metal catalysts
More informationPhysical Properties. Alcohols can be: CH CH 2 OH CH 2 CH 3 C OH CH 3. Secondary alcohol. Primary alcohol. Tertiary alcohol
Chapter 10: Structure and Synthesis of Alcohols 100 Physical Properties Alcohols can be: CH 3 CH 3 CH CH 2 OH * Primary alcohol CH 3 OH CH * CH 2 CH 3 Secondary alcohol CH 3 CH 3 * C OH CH 3 Tertiary alcohol
More informationLecture 17 February 14, 2013 MH + bonding, metathesis
Lecture 17 February 14, 2013 MH + bonding, metathesis Nature of the Chemical Bond with applications to catalysis, materials science, nanotechnology, surface science, bioinorganic chemistry, and energy
More informationMOLECULAR REPRESENTATIONS AND INFRARED SPECTROSCOPY
MOLEULAR REPRESENTATIONS AND INFRARED SPETROSOPY A STUDENT SOULD BE ABLE TO: 1. Given a Lewis (dash or dot), condensed, bond-line, or wedge formula of a compound draw the other representations. 2. Give
More informationN-Heterocyclic carbenes (NHCs): A comprehensive organocatalyst & reagent
N-Heterocyclic carbenes (NHCs): A comprehensive organocatalyst & reagent Gowrisankar Parthasarathy Leibniz Universität Hannover, Institut für Organische Chemie AK Kalesse group seminar 1 Outline Introduction
More informationExam (6 pts) Show which starting materials are used to produce the following Diels-Alder products:
Exam 1 Name CHEM 212 1. (18 pts) Complete the following chemical reactions showing all major organic products; illustrate proper stereochemistry where appropriate. If no reaction occurs, indicate NR :
More informationChapter 22 Amines. Nomenclature Amines are classified according to the degree of substitution at nitrogen.
CH. 22 Chapter 22 Amines Amines are very important in biological chemistry. Most of the bases in biological acid-base reactions are amines. They are also very important nucleophiles in biochemical reactions.
More informationOxidative Addition/Reductive Elimination 1. Oxidative Addition
Oxidative Addition Oxidative Addition/Reductive Elimination 1 An oxidative addition reaction is one in which (usually) a neutral ligand adds to a metal center and in doing so oxidizes the metal, typically
More informationORGANIC - EGE 5E CH. 2 - COVALENT BONDING AND CHEMICAL REACTIVITY
!! www.clutchprep.com CONCEPT: HYBRID ORBITAL THEORY The Aufbau Principle states that electrons fill orbitals in order of increasing energy. If carbon has only two unfilled orbitals, why does it like to
More informationTransition-metal-catalyzed multicomponent coupling reactions with imines and carbon monoxide*
Pure Appl. Chem., Vol. 85, No. 2, pp. 377 384, 2013. http://dx.doi.org/10.1351/pac-con-12-10-15 2013 IUPAC, Publication date (Web): 21 January 2013 Transition-metal-catalyzed multicomponent coupling reactions
More informationStrained Molecules in Organic Synthesis
Strained Molecules in rganic Synthesis 0. Introduction ~ featuring on three-membered rings ~ Tatsuya itabaru (M) Lit. Seminar 08068 for cyclobutadienes : see Mr. Yamatsugu's Lit. Sem. 069 eat of Formation
More informationMetalloporphyrin. ~as efficient Lewis acid catalysts with a unique reaction-field~ and. ~Synthetic study toward complex metalloporphyrins~
Metalloporphyrin ~as efficient Lewis acid catalysts with a unique reaction-field~ and ~Synthetic study toward complex metalloporphyrins~ Literature Seminar Kenta Saito (D1) 1 Topics Chapter 1 ~as efficient
More informationAdvanced Organic Chemistry
D. A. Evans, G. Lalic Question of the day: Chemistry 530A TBS Me 2 C Me toluene, 130 C 70% TBS C 2 Me H H Advanced rganic Chemistry Me Lecture 16 Cycloaddition Reactions Diels _ Alder Reaction Photochemical
More informationCobalt- and Iron-Catalyzed Isomerization-Hydroboration of Branched Alkenes: Terminal Hydroboration with Pinacolborane and 1,3,2-Diazaborolanes
Cobalt- and Iron-Catalyzed Isomerization-Hydroboration of Branched Alkenes: Terminal Hydroboration with Pinacolborane and 1,3,2-Diazaborolanes Takahiko Ogawa, a Adam J. Ruddy, a Orson L. Sydora, *,b Mark
More informationNon-Linear Effects in Asymmetric Catalysis: A Useful Tool in Understanding Reaction Mechanisms. Group Meeting Aaron Bailey 12 May 2009
Non-Linear Effects in Asymmetric Catalysis: A Useful Tool in Understanding Reaction chanisms Group eting Aaron Bailey 12 May 2009 What is a Non-Linear Effect? In asymmetric catalysis, the ee (er) of the
More informationOxidative couplings of two nucleophiles
Oxidative Couplings of Hydrocarbons Oxidative couplings of two nucleophiles Oxidants involved: O 2 H 2 O 2 high h valent metals(copper salts) halides(iodine(Ⅲ) oxidants) Lei, A. W. Chem. Rev., 2011, 111,
More information2016 Pearson Education, Inc. Isolated and Conjugated Dienes
2016 Pearson Education, Inc. Isolated and Conjugated Dienes 2016 Pearson Education, Inc. Reactions of Isolated Dienes 2016 Pearson Education, Inc. The Mechanism Double Bonds can have Different Reactivities
More informationAdvanced Organic Chemistry
D. A. Evans, G. Lalic Chem 530A Chemistry 530A Advanced Organic Chemistry Lecture notes part 8 Carbanions Organolithium and Grignard reagents Organocopper reagents 1. Direct metalation 2. From radical
More informationInorganic Chemistry GARY L. MIESSLER DONALD A. TARR. St. Olaf College Northfield, Minnesota
Inorganic Chemistry GARY L. MIESSLER DONALD A. TARR St. Olaf College Northfield, Minnesota Contents PREFACE xiii 1 INTRODUCTION TO INORGANIC CHEMISTRY 1 1-1 What Is Inorganic Chemistry? 1 1-2 Contrasts
More informationTandem RCM Isomerization Cyclopropanation Reactions
Tandem RCM Isomerization Cyclopropanation Reactions AÄ lvaro Mallagaray, Gema Domínguez, Ana Gradillas, and Javier Pérez-Castells* ORGANIC LETTERS 2008 Vol. 10, No. 4 597-600 Facultad de Farmacia, Dpto.
More informationAlkynes Nomenclature of Alkynes
Chapter 7 Alkynes Alkynes - hydrocarbons containing a carbon-carbon triple bond (2 bonds) Acyclic alkanes = C n H 2n+2 Alkenes and cyclic alkanes = C n H 2n Alkynes (and cyclic alkenes) = C n H 2n-2 The
More informationRhodium Catalyzed Alkyl C-H Insertion Reactions
Rhodium Catalyzed Alkyl C-H Insertion Reactions Rh Rh Jeff Kallemeyn 5/17/05 1. Cyclopropanation The Versatile and Reactive Rhodium Carbene R + Et Rh 2 (Ac) 4 R C 2 Et N 2 2. [2,3] sigmatropic rearrangement
More information1/4/2011. Chapter 18 Aldehydes and Ketones Reaction at the -carbon of carbonyl compounds
Chapter 18 Aldehydes and Ketones Reaction at the -carbon of carbonyl compounds The Acidity of the Hydrogens of Carbonyl Compounds: Enolate Anions Hydrogens on carbons to carbonyls are unusually acidic
More informationSPECTROSCOPY MEASURES THE INTERACTION BETWEEN LIGHT AND MATTER
SPECTROSCOPY MEASURES THE INTERACTION BETWEEN LIGHT AND MATTER c = c: speed of light 3.00 x 10 8 m/s (lamda): wavelength (m) (nu): frequency (Hz) Increasing E (J) Increasing (Hz) E = h h - Planck s constant
More informationThe Free Atom. Electronegativity for carbon: 2.5 Electronegativity for hydrogen: 2.2. Atomic energy levels, valence orbital ionization energies (VOIE)
The Free Atom Atomic energy levels, valence orbital ionization energies (VOIE) Electronegativity for carbon: 2.5 Electronegativity for hydrogen: 2.2 The Free Atom Atomic energy levels, valence orbital
More informationAdditions to Metal-Alkene and -Alkyne Complexes
Additions to tal-alkene and -Alkyne Complexes ecal that alkenes, alkynes and other π-systems can be excellent ligands for transition metals. As a consequence of this binding, the nature of the π-system
More informationChem 263 Nov 3, 2016
hem 263 Nov 3, 2016 Preparation of Aldehydes from Acid alides? + l l acid chloride aka acyl chloride aldehyde Needed: 2 Actual eagents: 2 /Pd Al This is lithium tri-t-butoxy aluminum hydride, a very sterically
More informationN-Heterocyclic Carbene Catalysis via Azolium Dienolates: An Efficient Strategy for Enantioselective Remote Functionalizations
Angew. Chem. Int. Ed. 2017, 10.1002. 1 N-Heterocyclic Carbene Catalysis via Azolium Dienolates: An Efficient Strategy for Enantioselective Remote Functionalizations Reporter: En Li Supervisor: Prof. Yong
More informationright (A, B, and C Example A corresponds to the structure reported by the Chirik group).
Problem 1 (3 points) In 2004, a bimetallic Zr compound exhibiting side-on 2 binding was reported by Chirik and coworkers (ature, 2004, 427, pp. 527-530). The crystal structure of this compound was obtained,
More informationTOK: The relationship between a reaction mechanism and the experimental evidence to support it could be discussed. See
Option G: Further organic chemistry (15/22 hours) SL students study the core of these options and HL students study the whole option (the core and the extension material). TOK: The relationship between
More informationChapter 5. Nucleophilic aliphatic substitution mechanism. by G.DEEPA
Chapter 5 Nucleophilic aliphatic substitution mechanism by G.DEEPA 1 Introduction The polarity of a carbon halogen bond leads to the carbon having a partial positive charge In alkyl halides this polarity
More informationTips for taking exams in 852
Comprehensive Tactical Methods in rganic Synthesis W. D. Wulff 1) Know the relative reactivity of carbonyl compounds Tips for taking exams in 852 Cl > > ' > > ' N2 eg: 'Mg Et ' 1equiv. 1equiv. ' ' Et 50%
More informationTable 8.2 Detailed Table of Characteristic Infrared Absorption Frequencies
Table 8.2 Detailed Table of Characteristic Infrared Absorption Frequencies The hydrogen stretch region (3600 2500 cm 1 ). Absorption in this region is associated with the stretching vibration of hydrogen
More informationChemistry 335 Supplemental Slides: Interlude 1. Reduction: addition of hydrogen to the substrate. Oxidation: addition of oxygen to the substrate
Interlude 1: Oxidations, Reductions & Other Functional Group Interconversions (FGI) 1. Definition of Oxidation and Reduction For practical purposes in organic chemistry, oxidation and reduction are defined
More informationSupporting Information
Supporting Information Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst Benjamin K. Keitz, Koji Endo, Myles B. Herbert, Robert H. Grubbs* Arnold and Mabel Beckman Laboratories
More informationGeneral Infrared Absorption Ranges of Various Functional Groups
General Infrared Absorption Ranges of Various Functional Groups Frequency Range Bond Type of Compound cm -1 Intensity C Alkanes 2850-2970 Strong 1340-1470 Strong C Alkenes 3010-3095 Medium 675-995 Strong
More informationNegishi Coupling of Secondary Alkylzinc Halides with Aryl Bromides and Chlorides
Negishi Coupling of Secondary Alkylzinc alides with Aryl Bromides and Chlorides X X = Br, Cl 2 1 ZnBr 1, 2 = Alkyl Cat. Pd(OAc) 2 Ligand TF/Toluene rt or 60 o C 1 2 J. Am. Chem. Soc. 2009, ASAP Article
More informationRhenium-Catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage
henium-catalyzed Synthesis of Multisubstituted Aromatic Compounds via C-C Single-Bond Cleavage Kuninobu, Y.; Takata,.; Kawata, A.; Takai, K. rg. Lett. ASAP Et 5 6 cat. [ebr(c) 3 (thf)] 2 5 6 Current Literature
More informationDehydrogenation and Related Reactions Catalyzed by Iridium Pincer Complexes. Zehua Yang Apr.23, 2011
Dehydrogenation and Related Reactions Catalyzed by Iridium Pincer Complexes Zehua Yang Apr.23, 2011 Contents Introduction Dehydrogenation of Alkanes Dehydrogenation Involving Heteroatom-Hydrogen Bonds
More informationPETE 203: Properties of oil
PETE 203: Properties of oil Prepared by: Mr. Brosk Frya Ali Koya University, Faculty of Engineering, Petroleum Engineering Department 2013 2014 Lecture no. (2): Crude oil chemistry and composition 5. Crude
More informationDetailed Course Content
Detailed Course Content Chapter 1: Carbon Compounds and Chemical Bonds The Structural Theory of Organic Chemistry 4 Chemical Bonds: The Octet Rule 6 Lewis Structures 8 Formal Charge 11 Resonance 14 Quantum
More informationCh 20 Carboxylic Acids and Nitriles
Ch 20 Carboxylic Acids and Nitriles Carboxylic Acids (RCO 2 H) are compounds with an OH attached to a carbonyl. Nitriles (RC N) are compounds a carbon-nitrogen triple bond. Naming Carboxylic Acids 1. Replace
More informationBasics of Catalysis and Kinetics
Basics of Catalysis and Kinetics Nobel laureates in catalysis: Haber (1918) Ziegler and Natta (1963) Wilkinson, Fischer (1973) Knowles, Noyori, Sharpless (2001) Grubbs, Schrock, Chauvin (2006) Ertl (2007)
More informationN_HW1 N_HW1. 1. What is the purpose of the H 2 O in this sequence?
N_HW1 N_HW1 Multiple Choice Identify the choice that best completes the statement or answers the question. There is only one correct response for each question. 1. What is the purpose of the H 2 O in this
More information