Facile preparation of α-amino ketones from oxidative ring-opening of aziridines by pyridine N-oxide
|
|
|
- Mary Holland
- 6 years ago
- Views:
Transcription
1 Facile preparation of α-amino ketones from oxidative ring-opening of aziridines by pyridine -oxide rg. Biomol. Chem., 2007, 5, 3428 Luo, Z.-B.; Wu, J.-Y.; ou, X.-L.; Dai, L.-X. Ts toluene Ts 80 o C John Maciejewski Current literature 01/05/08 John Wipf Group 1 2/17/2008
2 α-amino ketones F Et 2 (S)-2-amino-1-phenylpropan-1-one atural product found in leaves of Catha edulis Forsk upintrivir Shown to treat symptoms assoc. with common cold J. rg. Chem. 1994, 59, 8288 Tetrahedron: Asymmetry 2005, 16, Cl Active against brucellosis (Malta fever) AAC 2007, 51, 3752 Caspase-3 Potent caspase inhibitors K i values Caspase nm 4.0 nm rg. Lett. 2005, 7, 3529 John Wipf Group 2 2/17/2008
3 α-amino ketone preparation ften important synthetic intermediates Boc 2 Synthesis 2007, 1, 55 (-)-aphanorphin ' key synthetic intermediate (D)-tyrosine Begin from chiral pool ther methodologies include the following: 3 C C 3 C 2 Et 1) Br 2 2) (C 3 ) 2 DEAD cat.* C 2 Et J. et. Chem. 1984, 21, 1509 rg. Lett. 2007, 9, 3671 Cinchona alkaloids afford α amino ketones in high enantioselectivity John Wipf Group 3 2/17/2008
4 Preparation of -oxides Mild oxidants, easily prepared MMPP* ucl 3 (cat.) 2 *magnesium monoperoxyphthalate J. rg. Chem., 2007, 72, 6653 Chem. Commun., 2002, 1040 ther methods of -oxide preparation include use of peracids, 2 2, and 2 with catalysts conditions Synthesis 1993, 3, 263 (and references therein) ~71 kcal/mol J. Chem. Thermodynamics 1995, 27, 391 John Wipf Group 4 2/17/2008
5 Applications for -oxides and not to be confused with -oxide (TMA) -oxide (M) nitroxyl free radical (TEMP) s 4 /M Upjohn dihydroxylation TPAP/M Ley oxidation Br DMS/TMA Ganem oxidation -oxides used to regenerate transition metal catalysts John Wipf Group 5 2/17/2008
6 Applications for oxides of sulfur Br DMS B S [2,3] Br S Kornblum oxidation J. Am. Chem. Soc., 1957, 79, 6562 B Applications with aziridines 1 2 C 2 3 DMS S 2 1 C C SMe 2 Tetrahedron 1970, 26, 4347 Aziridine opened with DMS, followed by loss of SMe 2 to afford amino ketone Drawbacks: DMS is often difficult to remove, in addition to noxious byproduct (SMe 2 ) John Wipf Group 6 2/17/2008
7 xidative ring-opening of aziridines ecent advances Ts IBX!-CD Ts J. rg. Chem., 2003, 68, 9119 IBX promotes amino ketone formation, which is facilitated by β-cd Ts CA/BS Ts 2 Tetrahedron Lett., 2005, 46, 4111 The CA/BS system allows selective oxidation to the amino ketone John Wipf Group 7 2/17/2008
8 xidative ring-opening of aziridines rg. Biomol. Chem., 2007, 5, Initial investigations tested 1-10 equiv. of DMS in C 2 Cl 2, TF, MeC, benzene, EtAc, and Et 2 Investigations using pyridine -oxide (1.2 equiv.) DMF at 80 o C provided the desired α-amino ketone in 60% yield Toluene at 80 o C proved to give best results (70-80% yields) Increasing oxidant loading to 2-3 equiv. did not improve yields John Wipf Group 8 2/17/2008
9 xidative ring-opening of aziridines Electron donating pyridines accelerated reaction, but did not increase yield Electron withdrawing pyridines resulted in trace product after 40 h Sterically hindered substrates such as collidine gave low yields Aliphatic amines gave low yields of α-amino ketones, with undesired amino alcohol in moderate yields John Wipf Group 9 2/17/2008
10 xidative ring-opening of aziridines xidation proceeds in good yields with 5- and 6-membered rings John Wipf Group 10 2/17/2008
11 xidative ring-opening of aziridines John Wipf Group 11 2/17/2008
12 xidative ring-opening of aziridines Mechanism of oxidation Mechanism explains formation of amino ketone, but not amino alcohol. Aliphatic amine oxides provide low yields of desired amino ketone, but moderate yields of amino alcohol John Wipf Group 12 2/17/2008
13 xidative ring-opening of aziridines Proposed mechanism of oxidation Ts C 3 C 3 C 3 Ts C 3 C 3 Ts Aliphatic amine oxides have acidic hydrogen, where pyridine -oxides do not Authors did not address (or reference) the mechanism for the formation of amino alcohols Interesting method for preparing amino alcohols John Wipf Group 13 2/17/2008
14 Summary and Conclusions xidative ring-opening of aziridines Pyridine -oxides are efficient reagents for the oxidative ring-opening of aziridines The desired α-amino ketones were obtained in good yields on various substrates Aliphatic -oxides primarily afford the amino alcohol over the α-amino ketone Future work includes the development of an asymmetric version (chiral amines?) John Wipf Group 14 2/17/2008
Highlights of Schmidt Reaction in the Last Ten Years
ighlights of Schmidt eaction in the Last Ten Years Dendrobates histrionicus Jack Liu ov. 18, 2003 Introduction Classical Schmidt reaction of aldehydes and carboxylic acids Classical Schmidt reaction of
CHEMISTRY Topic #8: Oxidation and Reduction Reactions Fall 2018 Dr. Susan Findlay
CEMISTRY 2600 Topic #8: xidation and Reduction Reactions Fall 2018 Dr. Susan Findlay xidation States of Carbon Carbon can have any oxidation state from -4 (C 4 ) to +4 (C 2 ). As a general rule, increasing
Palladium-Catalyzed Oxygenation of Unactivated sp 3 C-H Bonds
Palladium-Catalyzed xygenation of Unactivated sp 3 C- Bonds Pd(Ac) 2 5 mol% PhI(Ac) 2 1.1 eq. Pd 2 Ac Desai, L. P.; ull, K. L.; Sanford *, M. S. University of Michigan J. Am. Chem. Soc. 2004, 126, ASAP
Nine-Step Enantioselective Total Synthesis of (+)-Minfiensine
ine-step nantioselective Total Synthesis of (+)-Minfiensine Jones, S. B.; Simmons, B.; MacMillan, D. W. C.* J. Am. Chem. Soc. 2009, ASAP. DI: 10.1021/ja906472m Kara George Wipf Group - Current Literature
Asymmetric Copper-Catalyzed Synthesis of α-amino Boronate Esters from N-tert- Butanesulfinyl Aldimines
Asymmetric Copper-Catalyzed Synthesis of α-amino Boronate Esters from -tert- Butanesulfinyl Aldimines R BR 2 J. Am. Chem. Soc. 2008, 130, 6910. Melissa A. Beenen, Chihul An, and Jonathan A. Ellman rrent
Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain
Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain Nicolaou and Co-workers Angew. Chem. Int. Ed. 2005, 44, 3443
Manganese-Catalyzed Late- Stage Aliphatic C H Azidation
Wipf group current literature Manganese-Catalyzed Late- Stage Aliphatic C H Azidation J. Am. Chem. Soc. 2015, 137, 5300 5303 Xiongyi Huang, Tova M. Bergsten, and John T. Groves Department of Chemistry,
Scalable Total Syntheses of N-Linked Tryptamine Dimers by Direct Indole-Aniline Coupling: Psychotrimine and Kapakahines B and F
Scalable Total Syntheses of -Linked Tryptamine Dimers by Direct ndole-aniline Coupling: Psychotrimine and Kapakahines B and F tryptamine X electrophilic nitrogen source 2 methodology development innovative
Asymmetric Catalysis by Lewis Acids and Amines
Asymmetric Catalysis by Lewis Acids and Amines Asymmetric Lewis acid catalysis - Chiral (bisooxazoline) copper (II) complexes - Monodentate Lewis acids: the formyl -bond Amine catalysed reactions Asymmetric
Research in our group encompasses the following 4 areas in Synthetic Organic Chemistry.
Research in our group encompasses the following 4 areas in Synthetic Organic Chemistry. 1] Development of Asymmetric Catalysis 2] Total Synthesis of Natural products 3] Development of Novel Protecting-Group-Free
Negishi 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
Chiral Brønsted Acid Catalysis
Chiral Brønsted Acid Catalysis Aryl Aryl Aryl Aryl S CF 3 2 P Fe CF 3 CF 3 2 Jack Liu ov. 16, 2004 CF 3 Introduction Chiral Brønsted acid catalysis in nature: enzymes and peptides Chiral Brønsted acid
O + k 2. H(D) Ar. MeO H(D) rate-determining. step?
ame: CEM 633: Advanced rganic Chem: ysical Problem Set 6 (Due Thurs, 12/8/16) Please do not look up references until after you turn in the problem set unless otherwise noted. For the following problems,
Chiral Diol Promoted Boronates Addi3on Reac3ons. Lu Yan Morken Group Boston College
Chiral Diol Promoted Boronates Addi3on Reac3ons Lu Yan Morken Group Boston College Main Idea R R B or R R B Ar * exchange B * * or B Ar R 1 R 1 R 2 R 1 R 2 Products not nucleophilic enough nucleophilic
Chiral Catalysis. Chiral Catalyst. Substrate. Chiral Catalyst
Chiral Catalysis Chiral (stoichiometric) reagents are a very important class of compound but... eed a stoichiometric quantity of the chiral component Unless it is cheap or recoverable this is not very
Total Synthesis of (-)-Mersicarpine
Total Synthesis of (-)-Mersicarpine Rie akajima, Tsuyoshi gino, Satoshi Yokoshima, and Tohru Fukuyama. J. Am. Chem. Soc. ASAP Published online 1-7-2010 Eric E. Buck Current Literature January 23, 2010
Organocatalytic stereoselective [8+2] and [6+4] cycloadditions
![Organocatalytic stereoselective [8+2] and [6+4] cycloadditions](/thumbs/85/92727022.jpg "Organocatalytic stereoselective [8+2] and [6+4] cycloadditions")
rganocatalytic stereoselective [8+2] and [6+4] cycloadditions Joel Walker Current Literature March 4 th, 2017 Mose, R.; Preegel, G.; Larsen, J.; Jakobsen, S.; Iversen, E..; Jørgensen, K. A. Nature Chem.
11-Step Enantioselective Synthesis of ( )-Lomaiviticin Aglycon
11-Step Enantioselective Synthesis of ( )-Lomaiviticin Aglycon Seth B. erzon, Liang Lu, Christina M. Woo, and Shivajirao L. Gholap J. Am. Chem. Soc. ASAP DI 10.1021/ja200034b Melissa Sprachman Current
a-aminoallylation of Aldehydes with Ammonia: Stereoselective Synthesis of Homoallylic Primary Amines
a-aminoallylation of Aldehydes with Ammonia: Stereoselective Synthesis of omoallylic Primary Amines 1 3 2 3 ML n 1 2 2 3 Masaharu Sugiura, Keiichi irano and Shu Kobayashi JACS ASAP ryan Wakefield @ Wipf
Studies on Heck and Suzuki Reactions Catalyzed by Palladium(0) and Wacker- Type Oxidative Cyclization Catalyzed by Palladium(II)
Studies on eck and Suzuki Reactions Catalyzed by Palladium(0) and Wacker- Type xidative Cyclization Catalyzed by Palladium() Zuhui Zhang enmark Group Meeting 10/21/2008 1 Part ne: Palladium(0)-Catalyzed
Functionalization of C(sp 3 ) H Bonds Using a Transient Directing Group
Literature eport Functionalization of C(sp 3 ) Bonds Using a Transient Directing Group eporter: Mu-Wang Chen Checker: Yue Ji Date: 2016-04-05 Yu, J.-Q. et al. Science 2016, 351, 252-256. Scripps esearch
1. Theoretical Investigation of Mechanisms and Stereoselectivities of Synthetic Organic Reactions
1. Theoretical Investigation of Mechanisms and Stereoselectivities of Synthetic Organic Reactions 2. Copper Catalyzed One-Pot Synthesis of Multisubstituted Quinolinones Hao Wang Denmark Group Presentation
Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization
![Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization](/thumbs/82/85235286.jpg "Total Synthesis of (+/-)-Goniomitine via a Formal Nitrile/Donor-Acceptor Cyclopropane [3 + 2] Cyclization")
Total Synthesis of (+/-)-Goniomitine via a Formal itrile/donor-acceptor Cyclopropane [3 + 2] Cyclization (-)-Goniomitine Christian L. Morales and Brian Pagenkopf* rganic Letters, ASAP Current Literature
Suggested solutions for Chapter 41
s for Chapter 41 41 PBLEM 1 Explain how this synthesis of amino acids, starting with natural proline, works. Explain the stereoselectivity of each step after the first. C 2 C 2 3 CF 3 C 2 2 Pd 2 C 2 +
Chem 253 Problem Set 7 Due: Friday, December 3, 2004
Chem 253 roblem Set 7 ue: Friday, ecember 3, 2004 Name TF. Starting with the provided starting material, provide a concise synthesis of. You may use any other reagents for your synthesis. It can be assumed
Shi Asymmetric Epoxidation
Shi Asymmetric Epoxidation Chiral dioxirane strategy: R 3 + 1 xone, ph 10.5, K 2 C 3, H 2, C R 3 formed in situ catalyst (10-20 mol%) is prepared from D-fructose, and its enantiomer from L-sorbose oxone,
Lecture Topics: I. Electrophilic Aromatic Substitution (EAS)
Reactions of Aromatic Compounds Reading: Wade chapter 17, sections 17-1- 17-15 Study Problems: 17-44, 17-46, 17-47, 17-48, 17-51, 17-52, 17-53, 17-59, 17-61 Key Concepts and Skills: Predict and propose
Bioinspired Total Synthesis of Agelastatin A
Bioinspired Total Synthesis of Agelastatin A Jeremy Chris P. Reyes and Daniel Romo Benjamin R. Eyer Wipf Group-Current Literature August 25, 2012 Angewandte Chemie International Edition. 2012, 51(28),
Direct Organocatalytic Enantioselective Mannich Reactions of Ketimines: An Approach to Optically Active Quaternary α-amino Acid Derivatives
Direct rganocatalytic Enantioselective Mannich eactions of Ketimines: An Approach to ptically Active Quaternary α-amino Acid Derivatives Wei Zhang, Steen Saaby, and Karl Anker Jorgensen The Danish ational
Rhodium Carbenoids and C-H Insertion
hodium Carbenoids and C- Insertion Literature Talk Uttam K. Tambar March 1, 2004 8pm, oyes 147 h h h h h h irreversible reversible carbenoid 2 h2l4 1 h2l4 or h2l4 2 utline I. What is a Carbene? II. What
Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation
![Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation](/thumbs/94/118539468.jpg "Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] Cycloadditions and Late Stage C-H Oxidation")
Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2] ycloadditions and Late Stage - xidation hristopher M. Rasik and M. Kevin Brown Angew. hem. Intd.
Mechanism Problem. 1. NaH allyl bromide, THF N H
Mechanism Problem 1. a allyl bromide, TF 2. 9-BB (1.2 equiv), TF, rt; ame (1.2 equiv); t-buli (2.4 equiv), TMEDA (2.4 equiv) 30 to rt; allyl bromide; 30% 2 2, aq. a, 0 C (58% yield) Mechanism Problem 9-BB
Dr. P. Wipf Page 1 of 5 10/7/2009. Cl Ru. Kingsbury, J. S.; Harrity, J. P. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791.
Dr. P. Wipf Page 1 of 5 10/7/2009 Alkene Metathesis Grubbs II published The Catalysts Me Mo F 3C CF3 Me F 3C CF3 C(Me) 2 chrock, R. R.; Murdzek, J..; Bazan, G. C.; Robbins, J.; DiMare, M.; 'Reagan, M.
Highly 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,
Advanced 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
Total Synthesis of ( )-Himandrine
Total Synthesis of ( )-imandrine M. Movassaghi,* M. Tjandra and J. Qi J. Am. hem. Soc. 2009, 131, 9648-9650 Bz Adam T. oye urrent Literature ctober 3, 2009 Adam oye @ Wipf Group Page 1 of 22 10/3/2009
Additions 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
Total Syntheses of Minfiensine
Total Syntheses of Minfiensine Douany, A. B.; umphreys, P. G.; verman, L. E.*; Wrobelski, A. D., J. Am. Chem. Soc. 2008, ASAP. D: 10.1021/ja800163v Shen, L.; Zhang, M.; Wu, Y.; Qin, Y.*, Angew. Chem. nt.
Electrophilic Carbenes
Electrophilic Carbenes The reaction of so-called stabilized diazo compounds with late transition metals produces a metal carbene intermediate that is electrophilic. The most common catalysts are Cu(I)
Copper-catalyzed cleavage of benzyl ethers with diacetoxyiodobenzene and p-toluenesulfonamide
General Papers ARKIVC 2008 (xii) 103-108 Copper-catalyzed cleavage of benzyl ethers with diacetoxyiodobenzene and p-toluenesulfonamide Ling He a,b, Qin Wang a, Guo-Chuan Zhou b, Lei Guo b, and Xiao-Qi
Chiral Quest Technology for Asymmetric Hydrogenation Applications and Gaps
Chiral Quest Technology for Asymmetric Hydrogenation Applications and Gaps Dr Ian C. Lennon Senior Vice President, Global Business Development Chiral Quest Corp., Cambridge, UK ilennon@chiralquest.com
Asymmetric Synthesis of α-substituted Allyl Boranes and Their Application in the Synthesis of Iso-agatharesinol
Asymmetric Synthesis of αsubstituted Allyl oranes and Their Application in the Synthesis of Isoagatharesinol Yuang Yu Fang and Varinder K. Aggarwal University of ristol, UK Angew. Chem. Int. Ed. 2007,
Organic Tutorials 3 rd Year Michaelmas Transition Metals in Organic Synthesis: (General paper level) ! 1! Reading
rganic Tutorials 3 rd Year Michaelmas 2010 Transition Metals in rganic Synthesis: (General paper level) Reading 1. Lecture Course, and suggested references from this. 2. Clayden, Greaves, Warren and Wothers.
Reductive Elimination from High-Valent Palladium. Kazunori Nagao MacMillan Group Meeting
Reductive Elimination from igh-valent Palladium Kazunori agao MacMillan Group eting Why do people focus on rging with C activation Facile reductive elimination DG C palladacycle oxidant complex C etero
Total Synthesis of Oxazolomycin A
Total Synthesis of xazolomycin A Me xazolomycin A Me Eto, K.; Yoshino, M.; Takahashi K.; Ishihara, J.; atakeyama S. rg. Lett. 2011, 13, 5398 Dimas Paz Wipf group- Current Literature ctober 8, 2011 Dimas
Halogen Bond Applications in Organic Synthesis. Literature Seminar 2018/7/14 M1 Katsuya Maruyama
Halogen Bond Applications in Organic Synthesis Literature Seminar 2018/7/14 M1 Katsuya Maruyama 1 Contents 1. Introduction 2. Property of Halogen Bond 3. Application to Organic Synthesis 2 1. Introduction
Strategies for Catalytic Asymmetric Electrophilic a Halogenation of Carbonyl Compounds
Strategies for Catalytic Asymmetric Electrophilic a alogenation of Carbonyl Compounds 1 2 Y Catalyst [X + ] 1 X! 2 Y intermann, L. ; Togni, A. Angew. Chem. Int. Ed. 2000, 39, 4359 4362 amashima, Y.; Sodeoka,
Radical Reactions. Radical Stability!!! bond dissociation energies X Y X + Y. bond BDE (kcal/mol) bond BDE (kcal/mol) CH 3 CH 3 CH 2 95 O H R 2 C H
adical eactions adical Stability!!! bond dissociation energies X Y X Y bond BDE (kcal/mol) bond BDE (kcal/mol) C 3 104 108 C 3 C 2 98 110 95 2 C 102 (-) 93 (C-) 92 C 3 C 3 36 89 85 C 3 C 3 80 adical eactions
C H activation of aliphatic amines without unnecessary mask M2 Takaya Togo
C H activation of aliphatic amines without unnecessary mask 2017.11.25 M2 Takaya Togo 1 Outline 1.Introduction 2.Free amines as DG Discovery of new activation mode Mechanistic studies Application of the
Asymmetric Nucleophilic Catalysis
Asymmetric ucleophilic Catalysis Chiral catalyst X 2 Chiral catalyst X = alkyl, X 1 2 1 Vedejs, E.; Daugulis,. J. Am. Chem. Soc. 2003, 125, 4166-4173 Shaw, S. A.; Aleman,.; Vedejs, E. J. Am. Chem. Soc.
Use 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,
Construction of Chiral Tetrahydro-β-Carbolines: Asymmetric Pictet Spengler Reaction of Indolyl Dihydropyridines
Literature Report V Construction of Chiral Tetrahydro-β-Carbolines: Asymmetric Pictet Spengler Reaction of Indolyl Dihydropyridines Reporter Checker Date : Xiao-Yong Zhai : Xin-Wei Wang : 2018-04-02 You,
Spiro Monophosphite and Monophosphoramidite Ligand Kit
Spiro Monophosphite and Monophosphoramidite Ligand Kit metals inorganics organometallics catalysts ligands custom synthesis cgm facilities nanomaterials 15-5162 15-5150 15-5156 15-5163 15-5151 15-5157
Enantioselective Protonations
Enantioselective Protonations Marc Timo Gieseler 25.02.2013 15.03.2013 Group Seminar AK Kalesse 1 verview Introduction Enantioselective Protonation of Cyclic Substrates Enantioselective Protonation of
D. X. Hu Towards Catalytic Enantioselective Halogenation of Alkenes Burns Group
D. X. Hu Towards Catalytic Enantioselective Halogenation of Alkenes Burns Group Literature Review Organic Synthesis 10, 20, 50 Years from Now? Catalytic Enantioselective Halogenation October 6 th, 2012
Bifunctional Asymmetric Catalysts: Design and Applications. Junqi Li CHEM Sep 2010
Bifunctional Asymmetric Catalysts: Design and Applications Junqi Li CHEM 535 27 Sep 2010 Enzyme Catalysis vs Small-Molecule Catalysis Bronsted acid Lewis acid Lewis acid Bronsted base Activation of both
"-Amino Acids: Function and Synthesis
"-Amino Acids: Function and Synthesis # Conformations of "-Peptides # Biological Significance # Asymmetric Synthesis Sean Brown MacMillan Group eting ovember 14, 2001 Lead eferences: Cheng,. P.; Gellman,
Enantioselective 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
Total Synthesis of ( )-Virginiamycin M2
Total Synthesis of ( )-Virginiamycin M2 Jie Wu and James S. Panek, Angewandte Chemie International Edition, 2010, 49, 6165-6168 btained from the CDC Public ealth Image Library. Image credit: CDC/Dr. David
A Modular Approach to Polyketide Building Blocks: Cycloadditions of Nitrile Oxides and Homoallylic Alcohols
A Modular Approach to Polyketide Building Blocks: Cycloadditions of itrile xides and Homoallylic Alcohols rganic Letters, 2005, ASAP ina Lohse-Fraefel and Erick M. Carreira * H H H + ' 1. t-bucl, -78 C
Silenes in organic synthesis: a concise synthesis of (±)-epi-picropodophyllin
lenes in organic synthesis: a concise synthesis of (±)-epi-picropodophyllin obert D. C. Pullin, Jonathan D. Sellars, and Patrick G. Steel* rg. Biomol. Chem., 2007, 5, 3201-3206 H H C Adam Hoye Current
Chapter 15. Reactions of Aromatic Compounds. Electrophilic Aromatic Substitution on Arenes. The first step is the slow, rate-determining step
Electrophilic Aromatic Substitution on Arenes Chapter 15 Reactions of Aromatic Compounds The characteristic reaction of aromatic rings is substitution initiated by an electrophile halogenation nitration
Electrophilic Aromatic Substitution. Dr. Mishu Singh Department of chemistry Maharana Pratap Govt.P.G.College Hardoi
Electrophilic Aromatic Substitution Dr. Mishu Singh Department of chemistry Maharana Pratap Govt.P.G.College Hardoi 1 Recall the electophilic addition of HBr (or Br2) to alkenes H + nu cleophile H Br H
TMSCl imidazole DMF. Ph Ph OTMS. Michael reaction. Michael reaction Ph R 3. epoxidation O R
eaction using diarylprolinol silyl ether derivatives as catalyst 1) C Et K C 3, ) MgBr, TF TMS hexane, 0 o C TBS p- C 6 4, T C Et 85%, 99% ee Angew. Chem., nt. Ed., 44, 41 (005). rg. Synth., 017, 94, 5.
CH 3 TMG, DMF N H 3 CO 2 S. (PPh 3 ) 2 Pd 0
1. (a) rovide a reasonable mechanism for the following transformation. I S 2 C 3 C 3 ( 3 ) 2 2, CuI C 3 TMG, DMF 3 C 2 S TMG = Me 2 Me 2 ICu ( 3 ) 2 0 I S 2 C 3 S 2 C 3 Cu I 3 3 3 C 2 S I 3 3 3 C 2 S 3
Application of Two Direct C(sp 3 )-H Functionalizations for the Total Synthesis of (+)-Lactacystin
Application of Two Direct C(sp 3 )- Functionalizations for the Total Synthesis of (+)-Lactacystin two stereoselective C(sp 3 )- functionalisations 2 C S Ac (S)-pyroglutaminol (+)-lactacystin S. Yoshioka,
CHEM 203. Final Exam December 18, 2013 ANSWERS. This a closed-notes, closed-book exam. You may use your set of molecular models
CEM 203 Your name: Final Exam December 18, 2013 ANSWERS This a closed-notes, closed-book exam You may use your set of molecular models This test consists of 10 pages Time: 2h 30 min 1. / 20 2. / 20 3.
3.7. Pyridinium Chloro Chromate (PCC):
xidation 3.7. Pyridinium hloro hromate (P): 97 l l r r 3 r l P is a very important oxidising reagent which will give controlled oxidation in the case of primary alcohol. It does not give over oxidation
Suggested solutions for Chapter 40
s for Chapter 40 40 PBLEM 1 Suggest mechanisms for these reactions, explaining the role of palladium in the first step. Ac Et Et BS () 4 2 1. 2. K 2 C 3 evision of enol ethers and bromination, the Wittig
Initials: 1. Chem 633: Advanced Organic Chemistry 2011 Final Exam
Initials: 1 ame: Chem 633: Advanced rganic Chemistry 2011 Final Exam Please answer the following questions clearly and concisely. In general, use pictures and less than 10 words in your answers. Write
Palladium-Mediated Functionalization of Heteroaromatic Cations: Comparative Study on Quinolizinium Cations
Palladium-Mediated Functionalization of Heteroaromatic Cations: Comparative Study on Quinolizinium Cations Domingo Garcia-Cuadrado, Ana M. Cuadro, Bernado M. Barchin, Ana unez, Tatiana Caneque, Julio Alvarez-
ISCHIA ADVANCED SCHOOL OF ORGANIC CHEMISTRY
ewis acid activation ewis base activation ISCIA ADVACED SC F GAIC CEMISTY Dual in Enantioselective Synthesis of Cyanohydrins Me A A Me UM ewis base catalysis is the process by which an electronpair donor
Chem 14D Spring 2010 Garg Midterm 1 Review / Practice Problems
Some Topics to Study (very broad): Chem 14D Spring 2010 Garg Midterm 1 Review / Practice Problems Reactivity stuff Classify atoms as electrophilic or nucleophilic Definitions of nucleophiles/electrophiles
A Highly Efficient Organocatalyst for Direct Aldol Reactions of Ketones and Aldehydes
A ighly Efficient rganocatalyst for Direct Aldol Reactions of Ketones and Aldehydes Zhuo Tang, Zhi-ua Yang, Xiao-ua Chen, Lin-Feng Cun, Ai-Qiao Mi, Yao-Zhong Jiang, and Liu-Zhu Gong Contribution from the
Chiral Brønsted Acid Catalysis
another. 1 One interesting aspect of chiral Brønsted acid catalysis is that the single s orbital of hydrogen Chiral Brønsted Acid Catalysis Reported by Matthew T. Burk December 3, 2007 INTRODUCTION The
Organic Chemistry. M. R. Naimi-Jamal. Faculty of Chemistry Iran University of Science & Technology
Organic Chemistry M. R. Naimi-Jamal Faculty of Chemistry Iran University of Science & Technology Chapter 5-2. Chemistry of Benzene: Electrophilic Aromatic Substitution Based on McMurry s Organic Chemistry,
VI. Metal alkyls from oxidative addition / insertion
V. Metal alkyls from oxidative addition / insertion A. Carbonylation - C insertion very facile, metal acyls easily cleaved, all substrates which undergo oxidative addition can in principle be carbonylated.
Nilson, M. G.; Funk, R. L. Org. Lett. 2010, ASAP. Chad Hopkins Wipf Group Literature Presentation
TtlS Total Synthesis of ( ) akadomarin kd A ilson, M. G.; Funk, R. L. rg. Lett. 2010, ASAP. Chad opkins Wipf Group Literature Presentation 10 23 10 Chad opkins @ Wipf Group Page 1 of 11 12/5/2010 Isolation
Zr-Catalyzed Carbometallation
-Catalyzed Carbometallation C C C C ML n C C ML n ML n C C C C ML n ML n C C ML n Wipf Group esearch Topic Seminar Juan Arredondo November 13, 2004 Juan Arredondo @ Wipf Group 1 11/14/2004 Carbometallation
Chapter 15 Reactions of Aromatic Compounds
Chapter 15 1 Chapter 15 Reactions of Aromatic Compounds Electrophilic Aromatic Substitution Arene (Ar-H) is the generic term for an aromatic hydrocarbon The aryl group (Ar) is derived by removal of a hydrogen
Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp 2 Zr(H)Cl: Scope and Mechanistic Insight
Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp 2 Zr(H)Cl: Scope and Mechanistic Insight Jared T. Spletstoser, Jonathan M. White, Ashok Rao Tunoori, and Gunda I. George J. Am. Chem.
12/27/2010. Chapter 15 Reactions of Aromatic Compounds
Chapter 15 Reactions of Aromatic Compounds Electrophilic Aromatic Substitution Arene (Ar-H) is the generic term for an aromatic hydrocarbon The aryl group (Ar) is derived by removal of a hydrogen atom
Aromatic Compounds II
2302272 Org Chem II Part I Lecture 2 Aromatic Compounds II Instructor: Dr. Tanatorn Khotavivattana E-mail: tanatorn.k@chula.ac.th Recommended Textbook: Chapter 17 in Organic Chemistry, 8 th Edition, L.
Aziridine Carboxylates, Carboxamides and Lactones: New Methods for Their Preparation and Their Transformation into α- and β-amino Acid Derivatives
Molecules 2000, 5 293 Aziridine Carboxylates, Carboxamides and Lactones: ew Methods for Their Preparation and Their Transformation into α- and β-amino Acid Derivatives obert H. Dodd Institut de Chimie
Lecture 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
Atovaquone: An Antipneumocystic Agent
Atovaquone: An Antipneumocystic Agent Atovaquone is a pharmaceutical compound marketed in the United States under different combinations to prevent and treat pneumocystosis and malaria. In a report from
π-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
Copper-Catalyzed Synthesis of Esters from Ketones. Alkyl Group as a Leaving Group.
Copper-Catalyzed Synthesis of Esters from Ketones. Alkyl Group as a Leaving Group. akatani, Y.; Koizumi, Y.; Yamasaki, R.; Saito, S. rg. Lett. 2008, 10, 2067-2070. An Annulation Reaction for the Synthesis
CHEM 203. Final Exam December 15, 2010 ANSWERS. This a closed-notes, closed-book exam. You may use your set of molecular models
CEM 203 Final Exam December 15, 2010 Your name: ANSWERS This a closed-notes, closed-book exam You may use your set of molecular models This test contains 15 pages Time: 2h 30 min 1. / 16 2. / 15 3. / 24
Chiral Catalyst II. Palladium Catalysed Allylic Displacement ( -allyl complexes) 1. L n Pd(0) 2. Nuc
Chiral Catalyst II ast lecture we looked at asymmetric catalysis for oxidation and reduction Many other organic transformations, this has led to much investigation Today we will look at some others...
ANSWER GUIDE APRIL/MAY 2006 EXAMINATIONS CHEMISTRY 249H
AWER GUIDE APRIL/MAY 2006 EXAMIATI CEMITRY 249 1. (a) PDC / C 2 2 (b) t-bume 2 i (1 equiv) / imidazole (1 equiv) i TBDM protection of the less sterically hindered alcohol (c) BuLi (1 equiv) then (d) 2
Glyoxylic acid derivatives in asymmetric synthesis*
Pure Appl. Chem., Vol. 72, No. 9, pp. 1589 1596, 2000. 2000 IUPAC Glyoxylic acid derivatives in asymmetric synthesis* Janusz Jurczak 1,2 and Tomasz Bauer 1 1 Department of Chemistry, University of Warsaw,
Stereoselective reactions of enolates
1 Stereoselective reactions of enolates Chiral auxiliaries are frequently used to allow diastereoselective enolate reactions Possibly the most extensively studied are the Evan s oxazolidinones These are
Recent Advancements in Outer Coordination Sphere Asymmetric Transfer Hydrogenation Emphasis on the Reduction of Prochiral Ketones and Imines
Recent Advancements in uter Coordination Sphere Asymmetric Transfer ydrogenation Emphasis on the Reduction of Prochiral Ketones and Imines Samantha Taffner Michigan State University ovember 30, 2005 utline
R.M. Williams. S Me O R H
C549.M. Williams xidations in ynthetic rganic Chemistry The Moffat and wern xidation eactions The classical Moffat oxidation (see: Pfitzner, K.E.; Moffatt, J.G., J. Am. Chem. oc. 1963, 85, 3027~3028),
Rhenium-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
i-pr 2 Zn CHO N Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Angew. Chem., Int. Ed. Engl. 2004, 43, 4490
Asymmetric Synthesis Utilizing Circularly Polarized Light Mediated by the otoequilibration of Chiral lefins in Conjuction with Asymmetric Autocatalysis l-cpl r-cpl (S) () Sato, I.; Sugie,.; Matsueda, Y.;
Direct Oxidative Heck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans
Direct xidative eck Cyclizations: Intramolecular Fujiwara-Moritani Arylations for the Synthesis of Functionalized Benzofurans and Dihydrobenzofurans by Zhang,.; Ferreira, E. M.; Stoltz, B. M. Angewandte
Synthesis of Nitriles a. dehydration of 1 amides using POCl 3 : b. SN2 reaction of cyanide ion on halides:
I. Nitriles Nitriles consist of the CN functional group, and are linear with sp hybridization on C and N. Nitriles are non-basic at nitrogen, since the lone pair exists in an sp orbital (50% s character
PART-I Development of New Synthetic Methodologies Using Heterogeneous Catalysts or Polyethylene Glycol
PAT-I Development of New Synthetic Methodologies Using eterogeneous Catalysts or Polyethylene Glycol Chapter 1.1.1 eterogeneous catalysts in organic synthesis: Introduction There have been a number of