Alexakis / Krause / Woodward Copper-Catalyzed Asymmetric Synthesis

1. Auflage 2013
ISBN: 978-3-527-66460-3
Verlag: Wiley-VCH
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 472 Seiten, E-Book

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.

Autoren/Hrsg.

Alexakis, Alexandre

Krause, Norbert

Woodward, Simon

Inhaltsverzeichnis

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

Über Autor(innen)

Alexandre Alexakis is Professor of Organic Chemistry at the University of Geneva, Switzerland. He received his PhD from Paris VI University in 1975, and following a two-year postdoctoral at Johns Hopkins University, Baltimore, USA, joined the CNRS at Pierre et Marie Curie University, where he was appointed Head of Research in 1985. In 1996 he became a full professor at Pierre et Marie Curie University, before moving to the University of Geneva in 1998. Professor Alexakis is a recipient of the Silver Medal of the CNRS, as well as the Novartis Lectureship Award, and has authored 300 articles. His research focuses on asymmetric synthesis and methodologies, using both metal catalysts, particularly copper reagents, and non-metallic catalysts.

 

Norbert Krause received his PhD from the Technical University of Braunschweig, Germany in 1986. After postdoctoral stays at the ETH Zürich and Yale University, he joined TU Darmstadt where he obtained his lecturing qualification in 1993. The following year he moved to the University of Bonn as an associate professor, before taking up his present position as a full professor at Dortmund University of Technology in 1998. He has been a fellow of the Japan Society for the Promotion of Science, a guest professor at the Université Catholique de Louvain, Belgium, the University of California, Santa Barbara, USA, and at the École Supérieure de Physique et de Chimie Industrielles de la Ville de Paris, France. Professor Krause has been on the editorial board of the European Journal of Organic Chemistry between 2006 and 2013. His research focuses on the stereoselective synthesis and transformation of functionalized allenes, taking advantage of coinage metal catalysis.

 

Simon Woodward is a Professor in Synthetic Organic Chemistry at Nottingham University, UK, and has authored over 120 publications in the areas of organic methodology, organometallic chemistry, and selective/ asymmetric catalysis. He has been Director of both the European Ligand Bank and an International Marie Curie PhD School in Catalysis of Organic Reactions incorporating the universities of Nottingham, Geneva, Sassari, and Dortmund. Professor Woodward also chaired the European Cooperation in Science and Technology Action D40 in Innovative Catalysis and is a member of related Action CM0903 in Biomass Utilisation. His research group is greatly enhanced by extensive collaboration with over 20 other groups, involved in the selective catalysis of organic reactions, throughout Europe and beyond.