Classics in Stereoselective Synthesis

1. Auflage 2008
ISBN: 978-3-527-29966-9
Verlag: WILEY-VCH

Buch, Englisch, 632 Seiten, Format (B × H): 183 mm x 241 mm, Gewicht: 1406 g

Die wichtigsten und nützlichsten Methoden der modernen stereoselektiven Synthese sind in diesem Band zusammengefasst. Viele anschauliche Beispiele für die Darstellung von Wirkstoffen und Naturstoffen regen zur gezielten Abwandlung und Integration in eigene Synthesewege an. Dabei geht es den Autoren weniger darum, das Gebiet in seiner Gesamtheit darzustellen; vielmehr versuchen sie, die wirklich grundlegenden Ansätze auszuwählen, die jeder organische Synthesechemiker kennen und anwenden sollte.

Autoren/Hrsg.

Carreira, Erick M.

Kvaerno, Lisbet

Fachgebiete

• Naturwissenschaften Chemie Physikalische Chemie Quantenchemie, Theoretische Chemie

Inhaltsverzeichnis

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

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

Über Autor(innen)

Carreira, Erick M.
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.

Kvaerno, Lisbet
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.

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.