The synthesis of molecules containing quaternary stereogenic centers via the intramolecular asymmetric Heck reaction. Eric Gillis 4/19/07
|
|
|
- Randolf Ford
- 5 years ago
- Views:
Transcription
1 The synthesis of molecules containing quaternary stereogenic centers via the intramolecular asymmetric Heck reaction Eric Gillis 4/19/07
2 Quaternary stereocenters in complex small molecules
3 Retrosynthetic strategies Many quaternary stereocenter architectures exist thods for catalytic asymmetric synthesis of quaternary stereocenters are varied: C-C bond forming Desymmetrization Rearrangement
4 Retrosynthetic strategies Acyclic quaternary stereocenters are accessed via allylation, allylic alkylation or Michael addition: Denmark, S. E. and Fu, J. Org. Lett. 2002, 4, Kacprzynski, M. and Hoveyda, A. H. J. Am. Chem. Soc. 2004, 126, Wu, J.; Mapreian, D. M., Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127,
5 Retrosynthetic strategies Cyclic quaternary centers are accessed via a number of methods: Doyle, A. G. and Jacobsen, E. N J. Am. Chem. Soc. 2005, 127, Overman, L. E. et al. J. Am. Chem. Soc. 1998, 120, Hamada, T.; Chieffi, A.; Ahman, J.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124,
6 Retrosynthetic strategies Fused bicyclic quaternary centers are accessed via desymmetrizing reactions: Wu, M. H.; Hansen, K. B.; Jacobsen, E. N. Angew. Chem. Int. Ed. 1999, 38, Sato, Y.; Honda, T.; Shibasaki, M. Tetrahedron Lett., 1992, 18,
7 Retrosynthetic strategies Spiro quaternary centers are accessed via the intramolecular Heck reaction: Ishihara, J.; Shimada, Y.; Tojo, S.; Murai, A. Synlett 2002, 3, Overman, L. E. et al. J. Am. Chem. Soc. 1998, 120,
8 Retrosynthetic strategies Bridged quaternary centers are accessed via the intramolecular Heck reaction:
9 Retrosynthetic strategies Unmet challenges in current methods: Generality Catalyst availability Low enantioselectivity The intramolecular asymmetric Heck reaction: Many architectures are accessible BINAP is generally effective Often enantioselectivity is 9:1
10 The Heck reaction Neutral pathway Cationic pathway
11 The intramolecular asymmetric Heck reaction Parameters in the intramolecular asymmetric Heck reaction: Sata, Y.; Sodeoka, M.; Shibasaki, M. J. Org. Chem. 1989, 54, Carpenter, N. E.; Kucera, D. J.; Overman, L. E. J. Org. Chem. 1989, 54,
12 chanistic complexity and diversity Stereodivergence Dynamic kinetic resolution Nucleophilic capture Tandem
13 Stereodivergence Z-alkene E-alkene Ashimori, A. and Overman, L. E. J. Org. Chem. 1992, 57, Ashimori, A.; Bachand, B.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, Overman, L. E et al. J. Am. Chem. Soc. 1998, 120,
14 Model for stereocontrol in the cationic pathway Favored Disfavored 3.2 Å 2.9 Å Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
15 Model for stereocontrol in the cationic pathway Favored Disfavored Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
16 Model for stereocontrol in the neutral pathway Proposed stereochemical influence/step: Disproved by: Oxidative addition Addn. of Ag + effects er β-hydride elimination Alkene geometry effects er Non-monomeric BINAP-Pd??? Migratory insertion, counter ion influence??? Migratory insertion, path A??? The neutral pathway: Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
17 Model for stereocontrol in the neutral pathway Chiral amplification study; catalyst is monomeric Pd-BINAP ee% product PMP Ag3PO4 Linear (PMP) Linear (Ag3PO4) ee% (R)-BINAP Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
18 Model for stereocontrol in the neutral pathway No solvent effect; counterion is fully dissociated Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
19 Model for stereocontrol in the neutral pathway Overman, L. E et al. J. Am. Chem. Soc. 1998, 120,
20 Model for stereocontrol in the neutral pathway Proposed stereochemical influence/step: Oxidative addition β-hydride elimination Non-monomeric BINAP-Pd Migratory insertion, counter ion influence Migratory insertion, path A Disproved by: Addn. of Ag + effects er Alkene geometry effects er No chiral amplification No solvent effect Low enantioselectivity with monodentate ligands The neutral pathway: Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
21 The effect of a halide additive Ashimori, A.; Bachand, B.; Calter, M. A.; Govek, S. P.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120,
22 chanistic complexity and diversity Stereodivergence Dynamic kinetic resolution Nucleophilic capture Tandem
23 Evidence for dynamic kinetic resolution Proposed mechanism: Lapierre, A. J. B.; Geib, S. J. and Curran, D. P. J. Am. Chem. Soc. 2007, 129, Curran, D. P et. al. Tetrahedron: Asymmetry 1997, 8,
24 chanistic complexity and diversity Stereodivergence Dynamic kinetic resolution Nucleophilic capture Tandem
25 Nucleophilic capture of Pd intermediate There are many examples of desymmetrizing Heck reactions: This reaction can be extended by capturing the Pd-intermediate with a nucleophile: Dounay, A. B. and Overman, L. E. Chem. Rev. 2003, 103, Oshima, T.; Kagechika, K.; Adachi. M.; Shibasaki, M. J. Am. Chem. Soc. 1996, 118,
26 Nucleophilic capture of Pd intermediate Proposed model for stereocontrol: Addition of NaBr was beneficial: Oshima, T.; Kagechika, K.; Adachi. M.; Shibasaki, M. J. Am. Chem. Soc. 1996, 118,
27 chanistic complexity and diversity Stereodivergence Dynamic kinetic resolution Nucleophilic capture Tandem
28 The total synthesis of ( )-physostigmine and ( )-physovenine Many natural products contain a hexahydropyrrolo[2,3-b]indole ring: R 3 N N H R 1 R 2 NHCO 2 N N H (!)-physotigmine NHCO 2 O N H (!)-physovenine An acetyl cholinesterase inhibitor used clinically for treatment of: glaucoma myasthenia gravis Alzheimer s disease Problems include narrow therapeutic window, short duration of action, unselective binding. Matsuura, T.; Overman, L. E. and Poon, D. J. J. Am. Chem. Soc. 1998, 120,
29 Retrosynthetic strategy Matsuura, T.; Overman, L. E. and Poon, D. J. J. Am. Chem. Soc. 1998, 120,
30 Retrosynthetic strategy Matsuura, T.; Overman, L. E. and Poon, D. J. J. Am. Chem. Soc. 1998, 120,
31 Forward synthesis Matsuura, T.; Overman, L. E. and Poon, D. J. J. Am. Chem. Soc. 1998, 120,
32 Forward synthesis Matsuura, T.; Overman, L. E. and Poon, D. J. J. Am. Chem. Soc. 1998, 120,
33 The total synthesis of ( )-capnellene Synthetic features All hydrocarbon 4 stereocenters (one quaternary) Fused cyclopentyl polycyclic framework Exocyclic olefin gem-dimethyl quaternary center Ohshima, T.; Kagachika, K.; Adachi, M.; Sodeoka, M.; Shibasaki, M. J. Am. Chem. Soc. 1996, 118,
34 Retrosynthetic strategy Ohshima, T.; Kagachika, K.; Adachi, M.; Sodeoka, M.; Shibasaki, M. J. Am. Chem. Soc. 1996, 118,
35 Forward synthesis Ohshima, T.; Kagachika, K.; Adachi, M.; Sodeoka, M.; Shibasaki, M. J. Am. Chem. Soc. 1996, 118,
36 Forward synthesis Ohshima, T.; Kagachika, K.; Adachi, M.; Sodeoka, M.; Shibasaki, M. J. Am. Chem. Soc. 1996, 118,
37 Conclusion / Future Directions H O HO H H 2,3-oxidosqualene dammaradienol
38 Acknowledgements Professor Silverman Professor Burke The 535 Class The Burke Group
The Synthesis of Molecules Containing Quaternary Stereogenic Centers via the Intramolecular Asymmetric Heck Reaction
The Synthesis of Molecules Containing Quaternary Stereogenic Centers via the Intramolecular Asymmetric Heck Reaction Reported by Eric P. Gillis April 19, 2007 INTRODUCTION The enantioselective synthesis
A 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
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
CHEM 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
Stereodivergent Catalysis. Aragorn Laverny SED Group Meeting July
Stereodivergent Catalysis Aragorn Laverny SED Group Meeting July 31 2018 1 Stereodivergent Catalysis In the context of asymmetric synthesis, a stereodivergent process is one that allows access to any given
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
Planar-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
Catalytic Asymmetric Total Syntheses of Quinine and Quinidine
Catalytic Asymmetric Total Syntheses of Quinine and Quinidine 8 7 9 2 1 3 4 6 5 7 9 8 2 1 3 4 6 5 Quinine Zhensheng Ding Quinidine January 22 2004 Chinese ew Year Day 1. Jacobsen, E.,. J. Am. Chem. Soc.
Molybdenum-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
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
Chapter 14. Principles of Catalysis
Organometallics Study Meeting 2011/08/28 Kimura Chapter 14. Principles of Catalysis 14. 1. General Principles 14.1.1. Definition of a Catalyst 14.1.2. Energetics of Catalysis 14.1.3. Reaction Coordinate
Catalytic Asymmetric Intramolecular. Reactions
Catalytic Asymmetric Intramolecular Pauson-Khand and Pauson-Khand-Type eactions Steven Ballmer CEM 535 Seminar ctober 9, 2008 University of Illinois at Urbana-Champaign pyright 2008 by Steven Ballmer Synthetic
Hybridization of Nickel Catalysis and Photoredox Catalysis. Literature seminar#1 B4 Hiromu Fuse 2017/02/04(Sat)
Hybridization of Nickel Catalysis and Photoredox Catalysis Literature seminar#1 B4 Hiromu Fuse 2017/02/04(Sat) Introduction Novel cross coupling was reported! Highly selective sp 3 C-H functionalization!
C 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
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
Catellani 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
Literature Report 2. Divergent Asymmetric Total Synthesis of Mulinane Diterpenoids. Date :
Literature Report 2 Divergent Asymmetric Total Synthesis of Mulinane Diterpenoids Reporter : Zhou-Hao Zhu Checker : Xiao-Yong Zhai Date : 2018-04-23 Liu, Y.-T.; Li, L.-P.; Xie, J.-H.*; Zhou, Q.-L. Angew.
Metal-catalyzed asymmetric hetero-diels-alder reactions of unactivated dienes with glyoxylates
Pure & Appl. Chern., Vol. 70, No. 5, pp. 11 17-1 122, 1998. Printed in Great Britain. (0 1998 IUPAC Metal-catalyzed asymmetric hetero-diels-alder reactions of unactivated dienes with glyoxylates Mogens
Stereoselective Organic Synthesis
Stereoselective rganic Synthesis Prabhat Arya Professor and Leader, Chemical Biology Program Dean, Academic Affairs, Institute of Life Sciences (An Associate Institute of University of yderabad Supported
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,
Stereoselective Organic Synthesis
Stereoselective rganic Synthesis Prabhat Arya Professor and Leader, Chemical Biology Program Dean, Academic Affairs, Institute of Life Sciences (An Associate Institute of University of yderabad Supported
Non-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
Dr. P. Wipf Chem /26/2007
I. Basic Principles I-L. Radicals & Carbenes Features of Radical Reactions Review: Curran, D. P. In Comprehensive Organic Synthesis; B. M. Trost and I. Fleming, Ed.; Pergamon Press: Oxford, 1991; Vol.
Homework for Chapter 17 Chem 2320
Homework for Chapter 17 Chem 2320 I. Cumulated, isolated, and conjugated dienes Name 1. Draw structures which fit the following descriptions. Use correct geometry! a conjugated diene with the formula C
A Summary of Organometallic Chemistry
A Summary of Organometallic Chemistry Counting valence electrons (v.e.) with the ionic model 1. Look at the total charge of the complex Ph 3 P Cl Rh Ph 3 P PPh 3 OC CO 2 Fe OC CO Co + charge:0 charge:
Nucleophilic Fluorination. Souvik Rakshit Burke group Literature Seminar July 13, 2013
Nucleophilic Fluorination Souvik Rakshit Burke group Literature Seminar July 13, 2013 Relevance 20% of pharmaceuticals contain fluorine 5-fluorouracil Antineoplastic agent, 1957 Lipitor (Atorvastatin)
Nuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320
Nuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320 I. Isolated, cumulated, and conjugated dienes A diene is any compound with two or C=C's is a diene. Compounds containing more than two
I. Introduction. Peng Zhao. Liu lab
Asymmetric Total Synthesis of Mycoleptodiscin A Shupeng Zhou, Hao Chen, Yijie Luo, Wenhao Zhang and Ang Li Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai
Course 201N 1 st Semester Inorganic Chemistry Instructor: Jitendra K. Bera
andout-9 ourse 201N 1 st Semester 2006-2007 Inorganic hemistry Instructor: Jitendra K. Bera ontents 3. rganometallic hemistry xidative Addition, Reductive Elimination, Migratory Insertion, Elimination
Total synthesis of Spongistatin
Literature Semminar 1. Introduction: Total synthesis of Spongistatin Chen Zhihua (M2) Isolation: Pettit et al. J. rg. Chem. 1993, 58, 1302. Kitagawa et al. Tetrahedron Lett. 1993, 34, 1993. Fusetani et
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
Palladium-catalyzed sp 3 C H activation. Yan Xu Dong Group Meeting Apr. 2, 2014
Palladium-catalyzed sp 3 C H activation, Yan Xu Dong Group Meeting Apr. 2, 2014 Content 1 Allylic C H activation 2 Benzylic C H activation Palladiumcatalyzed sp 3 C H activation 3 4 Common sp 3 C H activation:
Asymmetric 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:
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
Ahmad Masarwa Selective Metal-Mediated C-C Bond Activation of Strain Compounds: Application to Challenging non-natural Product Synthesis
Ahmad Masarwa Selective Metal-Mediated C-C Bond Activation of Strain Compounds: Application to Challenging non-natural Product Synthesis For the last few decades, organic chemists have spent much effort
Metalloporphyrin. ~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
sp 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)
Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang!
1! Domino Reactions in Total Synthesis! Reporter: Tianhe Yang! Supervisors: Prof. Yang! Prof. Chen! Prof. Tang! 2! utline! 1. Brief Introduction! 2. ucleophilic Dominoes! 3. Electrophilc Dominoes! 4. Radical
Regio- and stereocontrolled catalytic palladiumand nickel 'ene-type' cyclizations
Pure&Appl. Chern.,Vol. 62, No. 10, pp. 1941-1948,1990. Printed in Great Britain. 0 1990 IUPAC Regio- and stereocontrolled catalytic palladiumand nickel 'ene-type' cyclizations W. Oppolzer Departement de
Aza-Wacker-Type Cyclization. Group Meeting Tuesday, April 19, 2011 William Kuester
Aza-Wacker-Type Cyclization Group Meeting Tuesday, April 19, 2011 William Kuester N-heterocylization Reductive Amination Hydroamination Oxidative Cyclization Chemler, S.R. Org. Biomol. Chem. 2009, 7, 3009-3019.
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,
Palladium-Catalyzed Asymmetric Benzylic Alkylation Reactions
Palladium-Catalyzed Asymmetric Benzylic Alkylation Reactions Reporter: Hong-Qiang Shen Checker: Cong Liu Date: 2016/07/12 Masahiro Miura et al. Angew. Chem. Int. Ed. 2016, 55, 6973. Masahiro Miura Osaka
A. 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
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
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
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
Chemistry 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
Recent advances in transition metal-catalyzed or -mediated cyclization of 2,3-allenoic acids: New methodologies for the synthesis of butenolides*
Pure Appl. Chem., Vol. 76, No. 3, pp. 651 656, 2004. 2004 IUPAC Recent advances in transition metal-catalyzed or -mediated cyclization of 2,3-allenoic acids: New methodologies for the synthesis of butenolides*
Literature Report. A 11-Steps Total Synthesis of Magellanine through a Gold(І)-Catalyzed Dehydro Diels-Alder Reaction
Literature Report 11-Steps Total Synthesis of Magellanine through a Gold(І)-Catalyzed ehydro iels-lder Reaction Reporter: ong-qiang Shen Checker: Cong Liu ate: 2017/06/19 McGee, P.; Bétournay, G.; Barabé,
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.
II. Special Topics IIA. Enolate Chemistry & the Aldol Reaction
P. Wipf - Chem 2320 1 3/20/2006 II. Special Topics IIA. Enolate Chemistry & the Aldol Reaction Boger Notes: p. 147-206 (Chapter VIII) Carey/Sundberg: B p. 57-95 (Chapter B 2.1) Problem of the Day: Wang,
L.7. Mass Spectrum Interpretation
L.7. Mass Spectrum Interpretation Fragmentation reactions Spectrum interpretation Confirmation of ion structural assignment Biomolecule dissociation Fragmentation reactions 1. Fragmentation reactions of
Hydrogen-Mediated C-C Bond Formation
EPFL - ISIC - LSPN Hydrogen-Mediated C-C Bond Formation History and selected examples The Research of Prof. Michael Krische (University of Texas at Austin) LSPN Group Seminar Mathias Mamboury Table of
Ligand 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,
Rising Novel Organic Synthesis
Literature report Rising Novel Organic Synthesis Methods Based on the Cleavage of N-N and N-O Bonds Reporter: Zhang-Pei Chen Checker : Mu-Wang Chen Date: 04/03/2014 Kürti, L. et al. Kürti, L. et al. Science
Chiral Bronsted Acids as Catalysts
Chiral Bronsted Acids as Catalysts Short Literature Seminar 6/3/08 Dustin aup BIL Derived osphoric Acids - First reported in 1992 as a ligand by irrung and coworkers. 4 h 2 irrung Tet. Lett. 1992, 33,
Synthesis, Mechanism, and Properties of Cyclopenta-fused Polycyclic Aromatic Hydrocarbons. Chaolumen. Introduction
March 22, 2018 Synthesis, Mechanism, and Properties of Cyclopenta-fused Polycyclic Aromatic Hydrocarbons Reaxys Prize Club Symposium in Japan 2018 Chaolumen Institute for Chemical Research, Kyoto University
Transition Metal Catalyzed Carbon-Carbon Bond Activation
literature seminar 2 H. Mitsunuma(M1) 2010/09/08 Transition tal Catalyzed Carbon-Carbon Bond Activation 0. Introduction Currently, selective C-H and C-C bond activation by transition metal complexes has
Basic Organometallic Chemistry : Concepts, Syntheses, and Applications of Transition Metals. Table Of Contents: Foreword
Basic Organometallic Chemistry : Concepts, Syntheses, and Applications of Transition Metals Table Of Contents: Foreword v Preface vii List of abbreviations ix Chapter 1 Introduction 1 (15) 1.1 What is
Detailed 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
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...
Converting Cycloalkanones into N- Heterocycles: Formal Synthesis of ( )-Gephyrotoxin 287C. Claude Spino et al., J. Org. Chem. 2013, 78,
Converting Cycloalkanones into N- Heterocycles: Formal Synthesis of ( )-Gephyrotoxin 287C Claude Spino et al., J. Org. Chem. 2013, 78, 12532 12544. Poison frog alkaloids Isolated from poison frog skin.
Oxidative 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
σ Bonded ligands: Transition Metal Alkyls and Hydrides
σ Bonded ligands: Transition Metal Alkyls and Hydrides Simplest of organo-transitionmetal species Rare until and understanding of their stability in the 60 s and 70 s Metal alkyls can be considered as
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,
Chapter 5B. Functional Group Transformations: The Chemistry. Related Reactions
Chapter 5B Functional Group Transformations: The Chemistry of fcarbon-carbon C b π-bonds B d and Related Reactions Oxymercuation-Demercuration Markovnikov hydration of a double bond 1 Mechanism Comparision
The Vinylogous Aldol Reaction
The Vinylogous Aldol Reaction Reporter: Sixuan Meng Supervisor: Prof. Huang 2013-09-09 Zanardi, F. et al. Chem. Rev. 2000, 100, 1929 Zanardi, F. et al.. Chem. Rev. 2011, 111, 3076 Introduction 2 3 Regiochemical
Total Synthesis of (+)-Gelsemine. Xuan Dong group seminar 12/19/2012
Total Synthesis of (+)-Gelsemine Xuan Dong group seminar 12/19/2012 Historical Background of Gelsemine First detected the presence of alk aloids in extracts of G. sempervir ens in 1870 by Wormley. 1876,
14-1 Reactions Involving Gain or Loss of Ligands Reactions Involving Modification of Ligands
Organometallic Reaction and Catalysis 14-1 Reactions Involving Gain or Loss of Ligands 14-2 Reactions Involving Modification of Ligands 14-3 Organometallic Catalysts 14-4 Heterogeneous Catalysts Inorganic
Pd-Catalyzed Enantioselective Allylic Substitution: New Strategic Options for the Total Synthesis of Natural Products
Pd in Natural Product Synthesis Pd-Catalyzed Enantioselective Allylic Substitution: New Strategic Options for the Total Synthesis of Natural Products Timm Graening and Hans-Günther Schmalz* Keywords: asymmetric
Mechanistic Insides into Nickamine-Catalyzed Alkyl-Alkyl Cross-Coupling Reactions
Mechanistic Insides into Nickamine-Catalyzed Alkyl-Alkyl Cross-Coupling Reactions Abstract Within the last decades the transition metal-catalyzed cross-coupling of non-activated alkyl halides has significantly
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)
Enantioselective Formation of Quaternary Carbon Centers. Cory C. Bausch November 18, 2004
Enantioselective Formation of Quaternary Carbon Centers Cory C. Bausch ovember 18, 2004 Introduction Types of eactions utline Alkylations Diels-Alder Cyclopropanation Pd Catalyzed eactions Chiral Transfer
Department of Chemistry, University of Saskatchewan Saskatoon SK S7N 4C9, Canada. Wipf Group. Tyler E. Benedum Current Literature February 26, 2005
Ward, D.E; Jheengut, V.; Akinnusi, O.T. Enantioselective Direct Intermolecular Aldol Reactions with Enantiotopic Group Selectivity and Dynamic Kinetic Resolution, Organic Letters 2005, ASAP. Department
Dual Role of Silanol Groups in Cyclopropanation and Hiyama-Denmark Cross-Coupling Reactions
Dual Role of Silanol Groups in Cyclopropanation and Hiyama-Denmark Cross-Coupling Reactions L.-P. B. Beaulieu, L. B. Delvos, A. B. Charette* Département de Chimie, Université de Montréal, P.O. Box. 6138,
Insertion Reactions. 1) 1,1 insertion in which the metal and the X ligand end up bound to the same (1,1) atom
Insertion Reactions xidative addition and substitution allow us to assemble 1e and 2e ligands on the metal, respectively. With insertion, and its reverse reaction, elimination, we can now combine and transform
Reductive Elimination
Reductive Elimination Reductive elimination, the reverse of oxidative addition, is most often seen in higher oxidation states because the formal oxidation state of the metal is reduced by two units in
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
Chiral 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
N-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
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,
ORGANIC - CLUTCH CH ALCOHOLS, ETHERS, EPOXIDES AND THIOLS
!! www.clutchprep.com CONCEPT: ALCOHOL NOMENCLATURE Glycols: Alcohols with two hydroxyls are called ; with three hydroxyls are called Always give most priority to the OH group. EXAMPLE: Provide the correct
Suggested solutions for Chapter 32
s for Chapter 32 32 PBLEM 1 Explain how the stereo- and regio- chemistry of these reactions are controlled. Why is the epoxidation only moderately diastereoselective, and why does the amine attack where
Non-Enzymatic Enantioselective Polyene Cyclizations. Adam Hill Chem 535 May, 2 nd 2013
Non-Enzymatic Enantioselective Polyene Cyclizations Adam Hill Chem 535 May, 2 nd 2013 Enantioselective Polyene Cyclization (?) General Method to Rapidly Build Molecular Complexity (+) Exquisite Stereo-
Nucleophilic Heterocyclic Carbene Catalysis. Nathan Werner Denmark Group Meeting September 22 th, 2009
Nucleophilic Heterocyclic Carbene Catalysis Nathan Werner Denmark Group Meeting September 22 th, 2009 Thiamine Thiamine Vitamin B 1 The first water-soluble vitamin described Is naturally synthesized by
sp 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
The Story of Azadirachtin. Weiwu Ren
The Story of Azadirachtin Weiwu Ren 2015-12-17 Content 1 Introduction 2 Isolation and Structure Determination 3 Synthetic Study towards Azadirachtin 4 Total Synthesis of Azadirachtin Ley s Work Watanabe
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
ORGANIC - BROWN 8E CH ALKENES AND REACTIONS OF ALKENES
!! www.clutchprep.com CONCEPT: ALKENES and ALKYNES Alkenes/Alkynes are named by adding the suffix modifier (- /- ) to the end of the root. Alkenes/alkynes receive in numbering alkanes Location is assigned
Development of Chiral Phosphine Olefin Ligands and Their Use in Asymmetric Catalysis
Development of Chiral osphine lefin Ligands and Their Use in Asymmetric Catalysis 2 Wei-Liang Duan July 31, 2007 Research Works in Hayashi Group, Kyoto University (ct, 2003 Mar, 2007) Conventional Chiral
The Legends of the Star Tetrodotoxin
The Legends of the Star Tetrodotoxin Advisors: Prof. YANG Prof. CHEN Prof. TANG Reporter: Haixin YU History Puffer Fish Delicious food in Japan fugu Poisonous For Japanese and Egyptians Millennia For Europeans
Copper-mediated asymmetric transformations*
Pure Appl. Chem., Vol. 74, No. 1, pp. 37 42, 2002. 2002 IUPAC Copper-mediated asymmetric transformations* Alexandre Alexakis Department of Organic Chemistry, University of Geneva, 30 quai Ernest Ansermet,
Modern Synthetic Methods
Modern Synthetic Methods Dr. Dorian Didier dodich@cup.uni-muenchen.de Functionnalized Organometallic Reagents C-N, C-O and C-S Bond Formation Introduction to Organoboron Chemistry Introduction to Organosilicon
Topic Review Group meeting
Topic Review Group meeting Memory of chirality Christian Gloor Based on: Zhao, H.; Hsu, D. C.; Carlier, P.R. Synthesis 2005,1, 1. Table of content > Definitions of memory of chirality > Types of chirality
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
Olefin 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
Xiaopeng Yin The Wulff Group Michigan State University 6/6/2014. Career Summary. Eric N. Jacobsen
Xiaopeng Yin The Wulff Group Michigan State University 6/6/2014 Career Summary Eric N. Jacobsen About Eric N. Jacobsen PERSONAL Born February 22, 1960, New York, N.Y. Married to Virginia Estevez on May
Literature Report 2. Stereocontrolled Synthesis of Kalihinol C. Reiher, C. A.; Shenvi, R. A. J. Am. Chem. Soc. 2017, 139,
Literature Report 2 Stereocontrolled Synthesis of Kalihinol C Reporter: Huanping Xie Checker: Xiang Gao Date: 2017-04-17 Reiher, C. A.; Shenvi, R. A. J. Am. Chem. Soc. 2017, 139, 3647 3650. Contents 1
Huang, C.; Gevorgyan, V. J. Am. Chem. Soc. 2009, 131, Daniel Tzvi Cohen Short Literature Feb. 23, MeO HO OH. COOH ( )-Plicatic Acid OH OH
Asymmetric Total Synthesis of ( )-Plicatic Acid via a Highly Enantioselective and Diastereoselective Nucleophilic Epoxidation of Acyclic Trisubstituted lefins H H H H CH ( )-Plicatic Acid H H Sun, B.F.;
Chromium Arene Complexes
Go through Reviews Chem. Reviews Chem. Soc. Reviews Book by Prof. A. J. Elias Chromium Arene Complexes Complexation of Cr(CO) 3 with ARENES Chromium arene complexes Metal complexation is appealing in organic