Krause N. (ed.) Modern Organocopper Chemistry

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Krause N. (ed.) Modern Organocopper Chemistry

Wiley-VCH Verlag GmbH, 2002. - 368 p.
Organocopper chemistry is of wide applicability, very efficient and easy to perform. The main problem is to know the most appropriate reagent to use. The reader will find in this book all the details for the reagent of choice, for the scope and limitations, for the type of substrate needed. This book should be helpful not only to advanced research chemists, but also for teaching this chemistry to younger students in a comprehensive and modern way.

Contents
Structures and Reactivities of Organocopper Compounds
Johann T. B. H. Jastrzebski, Gerard van Koten
Introduction
Historical Perspective
The Oxidation States of Copper
Thermal Stability and Bonding in Organocopper (I) Compounds
Homoleptic Organocopper Compounds Cu_nR_n
Heteroleptic Organocopper Compounds Cu_n+mR_nX_m
Organocuprates
Neutral Homoleptic and Heteroleptic Organocuprates
Anionic Homoleptic and Heteroleptic Organocuprates
Lower- and Higher-order Cyanocuprates
Concluding Remarks Acknowledgement

Transmetalation Reactions Producing Organocopper Reagents
Paul Knochel, Bodo Betzemeier
Transmetalation of Functionalized Organolithium and Organomagnesium Reagents
Transmetalation of Organoboron and Organoaluminium Reagents
Transmetalation of Functionalized Organozinc Reagents
Preparation of Organozinc Reagents
Preparation of Organozinc Halides
Preparation of Diorganozinc Reagents
Substitution Reactions with Copper-Zinc Reagents
Addition Reactions with Copper-Zinc Reagents
Transmetalation of Organotin, Organosulfur, and Organotellurium Reagents
Transmetalation of Organotitanium and Organomanganese Reagents
Transmetalation of Organozirconium and Organosamarium Reagents
Conclusion

Heteroatomcuprates and a-Heteroatomalkylcuprates in Organic Synthesis 79
R. Karl Dieter
Heteroatomcuprates
GroupIV A Heteroatoms (Si, Ge, Sn)
Conjugate Addition Reactions
Silylcupration and Stannylcupration of Alkynes and Allenes
Substitution Reactions
GroupV A and VIA Heteroatoms (N, O, P)
α-Heteroatomalkylcuprates
GroupVI Heteroatoms (O, S, Se)
GroupV Heteroatoms (N, P) and Silicon
α-Fluoroalkylcuprates and α-Fluoroalkenylcuprates
Non-transferable Heteroatom(alkyl)cuprates and α-Heteroatomalkylcuprates
Simple Residual Ligands
Chiral Ligands

Copper-mediated Addition and Substitution Reactions of Extended Multiple Bond Systems
Norbert Krause, Anja Hoffmann-RoЁder
Copper-mediated Addition Reactions to Extended Michael Acceptors
Acceptor-substituted Dienes
Acceptor-substituted Enynes
Acceptor-substituted Polyenynes
Copper-mediated Substitution Reactions of Extended Substrates
Conclusion

Copper(I)-mediated 1,2- and 1,4-Reductions
Bruce H. Lipshutz

Introduction and Background
More Recent Developments: Stoichiometric Copper Hydride Reagents
1,4-Reductions Catalytic in Cu(I)
1,2-Reductions Catalyzed by Copper Hydride
Heterogeneous CuH-Catalyzed Reductions
Overview and Future Developments

Copper-mediated Diastereoselective Conjugate Addition and Allylic Substitution Reactions
Bernhard Breit, Peter Demel
Abstract
Conjugate Addition
Stereocontrol in Cyclic Derivatives
Stereocontrol in Acyclic Derivatives
γ-Heteroatom-substituted Michael Acceptors
γ-Alkyl-substituted a,b-Unsaturated Carbonyl Derivatives
α,β-Unsaturated Carbonyl Derivatives with Stereogenic Centers in Positions other than the γ-Position
Directed Conjugate Addition Reactions
Auxiliary-bound Chiral Michael Acceptors and Auxiliary Chiral Metal Complexes
Allylic Substitution

Copper-catalyzed Enantioselective Conjugate Addition Reactions of Organozinc Reagents
Ben L. Feringa, Robert Naasz, Rosalinde Imbos, Leggy A. Arnold
Organozinc Reagents
Copper-catalyzed 1,4-Addition
Phosphoramidite-based Catalysts
Catalytic Cycle
Variation of Ligands
Cyclic Enones
2-Cyclopentenone
Acyclic Enones
Synthetic Applications
Tandem Conjugate Addition-Aldol Reactions
Kinetic Resolution of 2-Cyclohexenones
Sequential 1,4-Additions to 2,5-Cyclohexadienones
Lactones
Nitroalkenes
Annulation Methodology

Copper-Mediated Enantioselective Substitution Reactions
A. Sofia E. KarlstroЁm, Jan-Erling BaЁckvall
Allylic Substitution
Allylic Substrates with Chiral Leaving Groups
Chiral Auxiliary that is Cleaved off after the Reaction
Catalytic Reactions with Chiral Ligands
Epoxides and Related Substrates
Concluding Remarks

Copper-Mediated Synthesis of Natural and Unnatural Products
Yukiyasu Chounan, Yoshinori Yamamoto

Abstract
Conjugate Addition 9
S_N2 Substitution
S_N20 Substitution
1,2-Metalate Rearrangements
Carbocupration

Mechanisms of Copper-mediated Addition and Substitution Reactions
Seiji Mori, Eiichi Nakamura
Conjugate Addition Reaction
Four-centered and Six-centered Mechanisms
Single-electron Transfer Theorem
Kinetic and Spectroscopic Analysis of Intermediates
Catalytic Conjugate Addition
Theoretically Based Conjugate Addition Reaction Pathway
Carbocupration Reactions of Acetylenes and Olefins
Experimental Facts
Theoretically Based Carbocupration Reaction Pathway
Substitution Reactions on Carbon Atoms
S_N2 Mechanism of Stoichiometric Substitution Reactions
S_N20 Allylation Reactions
Radical Substitution Reaction Mechanisms
Catalytic Substitution Reactions
Theoretically Based Alkylation Reaction Pathways
Other Issues
Counter-cation Lewis Acid Effects
Me3SiCl Acceleration
Dummy Ligands
The ‘‘Higher Order’’ Cuprate Controversy
Further Issues
Orbital Interactions in Copper-mediated Reactions
The Roles of Cluster Structure in Copper-mediated Reactions
Summary and Outlook

References
Subject Index