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Copper-Catalyzed Asymmetric Synthesis

Copper-Catalyzed Asymmetric Synthesis

Alexandre Alexakis (Editor), Norbert Krause (Editor), Simon Woodward (Editor)

ISBN: 978-3-527-33204-5

Mar 2014

472 pages

In Stock

$202.00

Description

This book reflects the increasing interest among the chemical synthetic community in the area of asymmetric copper-catalyzed reactions, and introduces readers to the latest, most significant developments in the field.

The contents are organized according to reaction type and cover mechanistic and spectroscopic aspects as well as applications in the synthesis of natural products. A whole chapter is devoted to understanding how primary organometallics interact with copper to provide selective catalysts for allylic substitution and conjugate addition, both of which are treated in separate chapters. Another is devoted to the variety of substrates and experimental protocols, while an entire chapter covers the use on non-carbon nucleophiles. Other chapters deal with less-known reactions, such as carbometallation or the additions to imines and related systems, while the more established reactions cyclopropanation and aziridination as well as the use of copper (II) Lewis acids are warranted their own special chapters. Two further chapters concern the processes involved, as determined by mechanistic studies. Finally, a whole chapter is devoted to the synthetic applications.

This is essential reading for researchers at academic institutions and professionals at pharmaceutical or agrochemical companies.
Introduction

THE PRIMARY ORGANOMETALLIC IN COPPER-CATALYZED REACTIONS
Scope and Introduction
Terminal Organometallics Sources Available
Coordination Motifs in Asymmetric Copper Chemistry
Asymmetric Organolithium-Copper Reagents
Asymmetric Grignard-Copper Reagents
Asymmetric Organozinc-Copper Reagents
Asymmetric Organoboron-Copper Reactions
Asymmetric Organoaluminium-Copper Reactions
Asymmetric Silane and Stannane Copper-Promoted Reagents
Conclusions

COPPER-CATALYZED ASYMMETRIC CONJUGATE ADDITION
Introduction
Conjugate Addition
Trapping of Enolates

COPPER-CATALYZED ASYMMETRIC CONJUGATE ADDITION AND ALLYLIC SUBSTITUTION OF ORGANOMETALLIC REAGENTS TO EXTENDED MULTIPLE-BOND SYSTEMS
Introduction
Copper-Catalyzed Asymmetric Conjugate Addition (ACA) to Polyconjugated Michael Acceptors
Copper-Catalyzed Asymmetric Allylic Substitution on Extended Multiple-Bond Systems
Conclusion

ASYMMETRIC ALLYLIC ALKYLATION
Introduction
Nucleophiles in Enantioselective Process Development
Functionalized Substrates
Desymmetrization of meso-Allylic Substrates
Kinetic Resolution Processes
Direct Enantioconvergent Transformation
Conclusion and Perspectives

RING OPENING OF EPOXIDES AND RELATED SYSTEMS
Introduction
Copper-Catalyzed Asymmetric Ring Opening of Epoxides with Amines
Copper-Catalyzed Asymmetric Ring Opening of Epoxides and Aziridines with Organometallic Reagents
Copper-Catalyzed Asymmetric Ring Opening of Heterobicyclic Systems with Organometallic Reagents
Conclusions

CARBON-BORON AND CARBON-SILICON BOND FORMATION
Introduction
C-B Bond Formation Reactions
C-Si Bond Formation Reactions
Summary

CuH IN ASYMMETRIC REDUCTIONS
Introduction
Asymmetric Conjugate Reductions
Asymmetric 1,2-Additions
Heterogeneous Catalysis
Conclusions and Perspectives

ASYMMETRIC CYCLOPROPANATION AND AZIRIDINATION REACTIONS
Introduction
Asymmetric Cyclopropanation
Asymmetric Aziridination
Conclusion

COPPER-CATALYZED ASYMMETRIC ADDITION REACTIONS OF IMINES
Introduction
Copper-Catalyzed Asymmetric Addition Reaction of Dialkylzinc to Imines
Copper-Catalyzed Asymmetric Allylation, Arylation, and Alkynylation Reactions of Imines
Copper as a Lewis Acid Catalyst for Asymmetric Reaction of Imines
Conclusions

CARBOMETALLATION REACTIONS
Introduction
Carbometallation of Cyclopropenes
Carbometallation of Alkynes
Summary

CHIRAL COPPER LEWIS ACIDS IN ASYMMETRIC TRANSFORMATIONS
Introduction
Cycloadditions
Claisen Rearrangements
Ene Reactions
Nucleophilic Addition to C=O and C=N Double Bonds
Conjugate Additions
Alpha-Functionalization of Carbonyl Compounds
Kinetic Resolution
Asymmetric Desymmetrization
Free-Radical Reactions
Conclusions

MECHANISTIC ASPECTS OF COPPER-CATALYZED REACTIONS
Introduction
Conjugate Addition
Allylic Alkylation and Substitution
Copper as Lewis Acid
1,2-Addition to Imines and Carbonyls
Copper Hydride
Cyclopropanation, Aziridination, and Allylic Oxidation

NMR SPECTROSCOPIC ASPECTS
Introduction
Copper Complexes with Phosphoramidite Ligands
Copper Complexes with TADDOL-Based Thiolate Ligands
Copper Complexes with Ferrocenyl-Based Ligands
Conclusion

APPLICATIONS TO THE SYNTHESIS OF NATURAL PRODUCTS
Introduction
Copper-Catalyzed Conjugate Additions in Natural Product Synthesis
Natural Product Synthesis Employing Asymmetric Allylic Alkylation
Asymmetric Copper-Catalyzed Diels-Alder Reactions
Asymmetric Copper-Catalyzed Mukaiyama Aldol Reactions
Other Asymmetric Copper-Catalyzed Aldol-Type Reactions
Asymmetric 1,3-Dipolar Cycloaddition and Claisen Rearrangement
Catalytic Asymmetric Cyclopropanation
Asymmetric Copper-Catalyzed Conjugate Reductions
Copper-Catalyzed Asymmetric 1,2-Type Addition Reactions
Miscellaneous Asymmetric Copper-Catalyzed Reactions
Conclusion

Index