Classics in Stereoselective Synthesis
1. Edition December 2008
XIX, 632 Pages, Hardcover
600 Pictures
3 tables
Textbook
ISBN:
978-3-527-32452-1
Wiley-VCH, Weinheim
Short Description
Concentrating on the most important and useful methods, this book provides illustrative examples of drug and natural product syntheses for use in the users' own work. This novel approach distills the truly groundbreaking reactions needed by every synthetic organic chemist.
Further versions
This book provides a noteworthy compilation of the groundbreaking methods of stereoselective synthesis, belonging to the repertoire of every modern practitioner of synthetic organic chemistry. The general principles underlying these processes are highlighted as they form the basis for the rapid and continuing developments in the field. The work also features illustrative examples of drug and natural product syntheses, resulting in a rich source of stimulating ideas for the efficient use of asymmetric reactions in the construction of stereochemically complex structures.
From the contents:
"Macrocyclic stereocontrol
"Carbonyl addition reactions
"alpha-Functionalization of enolates
"Aldol and allylation reactions
"Chiral acetals
"Alkene hydroboration, reduction, and oxidation
"Additions to C=N bonds and synthesis of amino acids
"Conjugate additions
"Chiral carbanions
"Metal-catalyzed allylations
"Cyclopropanations and CH-insertion reactions
"Sigmatropic rearrangements
"Diels-Alder and hetero-Diels-Alder reactions
"[3+2]- and [2+2]-cycloaddition reactions
MACROCYCLIC STEREOCONTROL
Introduction
Background
Conformational Control in Medium-Sized Rings
Asymmetric Synthesis with Medium-Sized Rings
Case Studies in Natural Products Total Synthesis
Macrocyclic Stereocontrol in Cyclic Peptides
Appendix: Macrocycle Formation
CARBONYL ADITION REACTIONS
Introduction
Non-Chelated 1,2-Asymmetric Induction and the Operation of Steric and Electronic Effects
1,2-Asymmetric Induction Predicated on Chelation Control
1,3-Asymmetric Induction from CBeta Stereogenic Centers
Asymmetric Induction by Remote Stereocenters (Beyond 1,3-Induction)
Catalytic Enantioselective Carbonyl Additions of Arganozinc Species
Enantioselective Ketone Reduction
Enzymatic Reduction of Ketones
Enantioselective Formation of Cyanohydrins
Enantioselective Alkyne Additions
Asymmetric Carbonyl-Ene Reactions
ALPHA-FUNCTIONALIZATIONS OF ENOLATES
Introduction
Diastereoselective Alpha-Alkylations of Chiral Enolates
Heteroatom-Substituted Enolates
Asymmetric Enolate Alkylations Using Chiral Auxiliaries
Enantioselective Enolate Alkylations
Alpha-Hydroxylations of Enolates
Alpha-Halogenations of Enolates
ALDOL REACTIONS
Introduction
Chiral Enolates Through the Use of Chiral Auxiliaries or Chiral Controller Groups
Substrate Control with Chiral Carbonyl Compounds
Catalytic Enantioselective Aldol Reactions
ALLYLATIONS OF C=O BONDS
Introduction
Reactivity of Allylmetal Reagents
Boronate Additions
Enantioselective Additions of Optically Active Allylic Boron Reagents
Diastereoselecive Allylations with Chiral Boron Reagents
Mechanistic Aspects - Lewis Acid-Promoted Addition of Allylsilanes and Allylstannanes to Aldehydes
Chelation Control in the Allylation of Alpha- and Beta-Alkoxy Aldehydes
Allylchromium Reagents
Diastereoselective Allylations with Chiral Silanes and Stannanes
Catalytic Asymmetric Allylations
CHIRAL ACETALS
Introduction
Diastereoselective Reactions of Chiral Acetals
Glycosylations
Spiroketals in Natural Product Synthesis
ALKENE HYDROBORATION
Introduction
Hydroborations with Acyclic Stereocontrol
Metal-Catalyzed Hydroborations
Asymmetric Hydroborations with Chiral Boranes
Catalytic Asymmetric Hydroboration, Hydrosilylation, and Hydroalumination
REDUCTIONS OF OLEFINS
Introduction
Diastereoselective Olefin Reductions by Catalytic Hydrogenation
Alternative Methods for Diastereoselective Olefin Reductions
Catalytic Asymmetric Olefin Hydrogenations
OXIDATIONS OF OLEFINS
Introduction
Diastereoselective Epoxidations
Enantioselective Epoxidations
Asymmetric Ring-Opening of Epoxides
Synthesis of Aziridines
Iodolactonizations and Other Olefin Cyclizations Induced by Electrophiles
Diastereoselective Dihydroxylations of Olefins
Enantioselective Dihydroxylations of Olefins
Enantioselective Aminohydroxylation of Olefins
AMINO ACIDS
Introduction
Enantioselective Hydrogenations of Alpha, Beta-Didehydroamino Acids
Enolate Alkylations in the Presence of Chiral Auxiliaries
Alkylation of Glycine Anion Equivalents in the Presence of Chiral Phase-Transfer Catalysts
Enolate Aminations
Enzymatic Syntheses of Alpha-Amino Acids
Catalytic Asymmetric Strecker Reactions
ADDITIONS TO C=N BONDS
Introduction
Substrate-Controlled Diastereoselective Additions to C=N Bonds
Additions to Imine Derivatives Bearing N-Bound Auxiliaries
Formation of Beta-Lactams Through Staudinger Reactions
Intramolecular Diastereoselective Iminium Ion Cyclizations
Pictet-Spengler Reactions
Catalytic Asymmetric Reductions of Imines and Imine Derivatives
Catalytic Enantioselective Mannich and Mannich-Type Reactions
Enantioselective Additions of Carbon Nucleophiles to C=N Bonds
CONJUGATE ADDITIONS
Introduction
Diastereoselective Conjugate Additions
Diastereoselective Conjugate Additions with Use of Chiral Auxiliaries
Enantioselective Conjugate Additions of Enolates and other Stabilized Carbon Nucleophiles
Enantioselective Conjugate Additions of Organometallic Species
Enantioselective Conjugate Additions of Radicals
Enantioselective Conjugate Additions of Heteroatom Nucleophiles
Conjugate Reductions
Catalytic Enantioselective Stetter Reactions
CHIRAL CARBONIONS
Introduction
Organolithium Reagents by Transmetalation of Organostannanes
Carbanions by Reductive Methods
Chiral Carbanions by Deprotonation
Sulfoxide- and Phosphorus-Stabilized Carbanions
Metal-Mediated Enantioselective Olefin Functionalizations
METAL-CATALYZED ALLYLATIONS
Introduction
Diastereoselective Palladium-Catalyzed Allylation Reactions
Enantioselective Palladium-Catalyzed Allylation Reactions
Iridium-Catalyzed Enantioselective Allylation Reactions
Copper-Catalyzed SN2' Allylation Reactions
Enantioselective Allylation Reactions Catalyzed by Other Transition Metals
Asymmetric Ring-Opening Reactions of Unsaturated Heterocycles
CYCLOPROPANATIONS AND C-H INSERTION REACTIONS
Introduction
Diastereoselective Cyclopropanations with Carbenoids Generated from Diazoalkanes
Enantioselective Dyclopropanations with Carbenoids Generated from Diazoalkanes
Diastereoselective Simmons-Smith Cyclopropanations
Enantioselective Simmons-Smith Cyclopropanations
Alternative Classes Cyclopropanations
Diastereoselective C-H Bonds
SIGMATROPIC REARRANGEMENTS
Introduction
Claisen and Claisen-Type [3,3]-Sigmatropic Rearrangements
Cope and Cope-Type [3,3]-Sigmatropic Rearrangements
[2,3]-Sigmatropic Rearrangements
Ene Reactions
Nazarov Cyclizations
DIELS-ALDER AND HETERO-DIELS-ALDER REACTIONS
Introduction
Diastereoselective Intermolecular Diels-Alder Reactions
Diastereoselective Intramolecular Diels-Alder Reactions
Diastereoselective Diels-Alder Reactions Using Chiral Auxiliaries
Catalytic Enantioselective Diels-Alder Reactions
Diastereoselective Hetero-Diels-Alder Reactions
Enantioselective Hetero-Diels-Alder Reactions
[3+2]- AND [2+2]-CYCLOADDITION REACTIONS
Introduction
Substrate-Controlled Diastereoselective [1,3]-Dipolar Cycloadditions
Diastereoselective [1,3]-Dipolar Cycloadditions Using Chiral Auxiliaries
Catalytic Enantioselective [1,3]-Dipolar Cycloadditions
[3+2]-Cycloadditions with Trimethylenemethane Equivalents
Ketene Cycloadditions
Photochemical [2+2]-Cycloadditions
Introduction
Background
Conformational Control in Medium-Sized Rings
Asymmetric Synthesis with Medium-Sized Rings
Case Studies in Natural Products Total Synthesis
Macrocyclic Stereocontrol in Cyclic Peptides
Appendix: Macrocycle Formation
CARBONYL ADITION REACTIONS
Introduction
Non-Chelated 1,2-Asymmetric Induction and the Operation of Steric and Electronic Effects
1,2-Asymmetric Induction Predicated on Chelation Control
1,3-Asymmetric Induction from CBeta Stereogenic Centers
Asymmetric Induction by Remote Stereocenters (Beyond 1,3-Induction)
Catalytic Enantioselective Carbonyl Additions of Arganozinc Species
Enantioselective Ketone Reduction
Enzymatic Reduction of Ketones
Enantioselective Formation of Cyanohydrins
Enantioselective Alkyne Additions
Asymmetric Carbonyl-Ene Reactions
ALPHA-FUNCTIONALIZATIONS OF ENOLATES
Introduction
Diastereoselective Alpha-Alkylations of Chiral Enolates
Heteroatom-Substituted Enolates
Asymmetric Enolate Alkylations Using Chiral Auxiliaries
Enantioselective Enolate Alkylations
Alpha-Hydroxylations of Enolates
Alpha-Halogenations of Enolates
ALDOL REACTIONS
Introduction
Chiral Enolates Through the Use of Chiral Auxiliaries or Chiral Controller Groups
Substrate Control with Chiral Carbonyl Compounds
Catalytic Enantioselective Aldol Reactions
ALLYLATIONS OF C=O BONDS
Introduction
Reactivity of Allylmetal Reagents
Boronate Additions
Enantioselective Additions of Optically Active Allylic Boron Reagents
Diastereoselecive Allylations with Chiral Boron Reagents
Mechanistic Aspects - Lewis Acid-Promoted Addition of Allylsilanes and Allylstannanes to Aldehydes
Chelation Control in the Allylation of Alpha- and Beta-Alkoxy Aldehydes
Allylchromium Reagents
Diastereoselective Allylations with Chiral Silanes and Stannanes
Catalytic Asymmetric Allylations
CHIRAL ACETALS
Introduction
Diastereoselective Reactions of Chiral Acetals
Glycosylations
Spiroketals in Natural Product Synthesis
ALKENE HYDROBORATION
Introduction
Hydroborations with Acyclic Stereocontrol
Metal-Catalyzed Hydroborations
Asymmetric Hydroborations with Chiral Boranes
Catalytic Asymmetric Hydroboration, Hydrosilylation, and Hydroalumination
REDUCTIONS OF OLEFINS
Introduction
Diastereoselective Olefin Reductions by Catalytic Hydrogenation
Alternative Methods for Diastereoselective Olefin Reductions
Catalytic Asymmetric Olefin Hydrogenations
OXIDATIONS OF OLEFINS
Introduction
Diastereoselective Epoxidations
Enantioselective Epoxidations
Asymmetric Ring-Opening of Epoxides
Synthesis of Aziridines
Iodolactonizations and Other Olefin Cyclizations Induced by Electrophiles
Diastereoselective Dihydroxylations of Olefins
Enantioselective Dihydroxylations of Olefins
Enantioselective Aminohydroxylation of Olefins
AMINO ACIDS
Introduction
Enantioselective Hydrogenations of Alpha, Beta-Didehydroamino Acids
Enolate Alkylations in the Presence of Chiral Auxiliaries
Alkylation of Glycine Anion Equivalents in the Presence of Chiral Phase-Transfer Catalysts
Enolate Aminations
Enzymatic Syntheses of Alpha-Amino Acids
Catalytic Asymmetric Strecker Reactions
ADDITIONS TO C=N BONDS
Introduction
Substrate-Controlled Diastereoselective Additions to C=N Bonds
Additions to Imine Derivatives Bearing N-Bound Auxiliaries
Formation of Beta-Lactams Through Staudinger Reactions
Intramolecular Diastereoselective Iminium Ion Cyclizations
Pictet-Spengler Reactions
Catalytic Asymmetric Reductions of Imines and Imine Derivatives
Catalytic Enantioselective Mannich and Mannich-Type Reactions
Enantioselective Additions of Carbon Nucleophiles to C=N Bonds
CONJUGATE ADDITIONS
Introduction
Diastereoselective Conjugate Additions
Diastereoselective Conjugate Additions with Use of Chiral Auxiliaries
Enantioselective Conjugate Additions of Enolates and other Stabilized Carbon Nucleophiles
Enantioselective Conjugate Additions of Organometallic Species
Enantioselective Conjugate Additions of Radicals
Enantioselective Conjugate Additions of Heteroatom Nucleophiles
Conjugate Reductions
Catalytic Enantioselective Stetter Reactions
CHIRAL CARBONIONS
Introduction
Organolithium Reagents by Transmetalation of Organostannanes
Carbanions by Reductive Methods
Chiral Carbanions by Deprotonation
Sulfoxide- and Phosphorus-Stabilized Carbanions
Metal-Mediated Enantioselective Olefin Functionalizations
METAL-CATALYZED ALLYLATIONS
Introduction
Diastereoselective Palladium-Catalyzed Allylation Reactions
Enantioselective Palladium-Catalyzed Allylation Reactions
Iridium-Catalyzed Enantioselective Allylation Reactions
Copper-Catalyzed SN2' Allylation Reactions
Enantioselective Allylation Reactions Catalyzed by Other Transition Metals
Asymmetric Ring-Opening Reactions of Unsaturated Heterocycles
CYCLOPROPANATIONS AND C-H INSERTION REACTIONS
Introduction
Diastereoselective Cyclopropanations with Carbenoids Generated from Diazoalkanes
Enantioselective Dyclopropanations with Carbenoids Generated from Diazoalkanes
Diastereoselective Simmons-Smith Cyclopropanations
Enantioselective Simmons-Smith Cyclopropanations
Alternative Classes Cyclopropanations
Diastereoselective C-H Bonds
SIGMATROPIC REARRANGEMENTS
Introduction
Claisen and Claisen-Type [3,3]-Sigmatropic Rearrangements
Cope and Cope-Type [3,3]-Sigmatropic Rearrangements
[2,3]-Sigmatropic Rearrangements
Ene Reactions
Nazarov Cyclizations
DIELS-ALDER AND HETERO-DIELS-ALDER REACTIONS
Introduction
Diastereoselective Intermolecular Diels-Alder Reactions
Diastereoselective Intramolecular Diels-Alder Reactions
Diastereoselective Diels-Alder Reactions Using Chiral Auxiliaries
Catalytic Enantioselective Diels-Alder Reactions
Diastereoselective Hetero-Diels-Alder Reactions
Enantioselective Hetero-Diels-Alder Reactions
[3+2]- AND [2+2]-CYCLOADDITION REACTIONS
Introduction
Substrate-Controlled Diastereoselective [1,3]-Dipolar Cycloadditions
Diastereoselective [1,3]-Dipolar Cycloadditions Using Chiral Auxiliaries
Catalytic Enantioselective [1,3]-Dipolar Cycloadditions
[3+2]-Cycloadditions with Trimethylenemethane Equivalents
Ketene Cycloadditions
Photochemical [2+2]-Cycloadditions
Erick M. Carreira, born in La Habana, Cuba, obtained a B.S. degree in 1984 from the University of Illinois at Urbana Champaign under the supervision of Scott E. Denmark, and a PhD in 1990 from Harvard University under the supervision of David A. Evans. After carrying out postdoctoral work with Peter Dervan at the California Institute of Technology through mid-1992, he joined the faculty at the same institution as an assistant professor of chemistry and was promoted to full professor in 1997. In 1998, he moved to the Laboratory of Organic Chemistry at the ETH-Zurich, Switzerland. He has over 180 research publications and numerous patents to his name. He is the recipient of, among others, the American Chemical Society Award in Pure Chemistry the Nobel Laureate Signature Award, and he has held the David and Lucile Packard Foundation Fellowship in Science and Engineering as well as the Tetrahedron Chair Prize. Professor Carreira's research program is focused on the four interrelated areas of organic synthesis: catalysis, methodology, natural products synthesis, and bioorganic chemistry.
Lisbet Kvaerno, born in Denmark, received her M.Sc. in chemistry from the University of Copenhagen under Prof. Jesper Wengel. She obtained her PhD in 2004 after working in total synthesis at the Technical University of Denmark under Prof. David Tanner and in medicinal chemistry at the ETH Zurich supervised by Prof. Erick M. Carreira. As a postdoctoral fellow in the research group of Prof. David A. Evans at Harvard University, she completed the total synthesis of the marine natural product (+)-azaspiracid. After a brief period as an independent junior group leader at the Max Planck Institute of Coal Research in Muelheim, Germany, she joined Lundbeck in Copenhagen as a process chemist in the late summer of 2008.
Lisbet Kvaerno, born in Denmark, received her M.Sc. in chemistry from the University of Copenhagen under Prof. Jesper Wengel. She obtained her PhD in 2004 after working in total synthesis at the Technical University of Denmark under Prof. David Tanner and in medicinal chemistry at the ETH Zurich supervised by Prof. Erick M. Carreira. As a postdoctoral fellow in the research group of Prof. David A. Evans at Harvard University, she completed the total synthesis of the marine natural product (+)-azaspiracid. After a brief period as an independent junior group leader at the Max Planck Institute of Coal Research in Muelheim, Germany, she joined Lundbeck in Copenhagen as a process chemist in the late summer of 2008.
