Copper-Catalyzed Asymmetric Synthesis -- Contents -- List of Contributors -- Introduction -- Chapter 1 The Primary Organometallic in Copper-Catalyzed Reactions -- 1.1 Scope and Introduction -- 1.2 Terminal Organometallics Sources Available -- 1.3 Coordination Motifs in Asymmetric Copper Chemistry -- 1.3.1 Classical Cuprate Structure and Accepted Modes of Reaction -- 1.3.1.1 Conjugate Addition -- 1.3.1.2 SN2 Allylation Reactions -- 1.3.2 Motifs in Copper-Main Group Bimetallics and Substrate Binding -- 1.4 Asymmetric Organolithium-Copper Reagents -- 1.5 Asymmetric Grignard-Copper Reagents -- 1.6 Asymmetric Organozinc-Copper Reagents -- 1.7 Asymmetric Organoboron-Copper Reagents -- 1.8 Asymmetric Organoaluminium-Copper Reagents -- 1.9 Asymmetric Silane and Stannane Copper-Promoted Reagents -- 1.10 Conclusions -- References -- Chapter 2 Copper-Catalyzed Asymmetric Conjugate Addition -- 2.1 Introduction -- 2.2 Conjugate Addition -- 2.2.1 The Nucleophile -- 2.2.2 The Copper Salt -- 2.2.3 The Ligand -- 2.2.4 Scope of Michael Acceptors -- 2.2.4.1 Enones -- 2.2.4.2 Enals -- 2.2.4.3 Nitroalkenes -- 2.2.4.4 α,β-Unsaturated Amide and Ester Derivatives -- 2.2.4.5 Other Michael Acceptors -- 2.2.5 Formation of All-Carbon Quaternary Stereocenters -- 2.3 Trapping of Enolates -- References -- Chapter 3 Copper-Catalyzed Asymmetric Conjugate Addition and Allylic Substitution of Organometallic Reagents to Extended Multiple-Bond Systems -- 3.1 Introduction -- 3.2 Copper-Catalyzed Asymmetric Conjugate Addition (ACA) to Polyconjugated Michael Acceptors -- 3.2.1 Background -- 3.2.2 1,6 Selectivity in ACA to Polyconjugated Systems -- 3.2.3 1,4 Selectivity in ACA to Polyconjugated Systems -- 3.3 Copper-Catalyzed Asymmetric Allylic Substitution on Extended Multiple-Bond Systems -- 3.3.1 Background.

3.3.2 Copper-Catalyzed Enantioselective Allylic Substitution on Extended Multiple-Bond Systems -- 3.4 Conclusion -- References -- Chapter 4 Asymmetric Allylic Alkylation -- 4.1 Introduction -- 4.2 Nucleophiles in Enantioselective Process Development -- 4.2.1 Grignard Nucleophiles -- 4.2.2 Diorganozinc Nucleophiles -- 4.2.3 Triorganoaluminium Nucleophiles -- 4.2.4 Organoboranes Nucleophiles -- 4.2.5 Organolithium Nucleophiles -- 4.3 Functionalized Substrates -- 4.3.1 Trisubstituted Substrates -- 4.3.2 Ester Derivatives -- 4.3.3 Heterofunctionalized Substrates -- 4.3.4 Vinylic Boronates and Silanes -- 4.3.5 Substrates Bearing Two Leaving Groups (1,4 or 1,1') -- 4.3.6 Enyne-Type Substrates -- 4.4 Desymmetrization of meso-Allylic Substrates -- 4.4.1 Polycyclic Hydrazines, Symmetric Allylic Epoxides, Oxabicyclic Alkenes -- 4.4.2 Cyclic Allylic Bis(Diethyl phosphates) -- 4.4.3 Miscellaneous Desymmetrization -- 4.5 Kinetic Resolution Processes -- 4.5.1 Allylic Epoxides and Aziridines, Oxabicyclic Alkenes, Bicyclic Oxazines -- 4.5.2 Stereodivergent Kinetic Resolution on Acyclic Allylic Halides -- 4.6 Direct Enantioconvergent Transformation -- 4.7 Conclusion and Perspectives -- References -- Chapter 5 Ring Opening of Epoxides and Related Systems -- 5.1 Introduction -- 5.2 Copper-Catalyzed Asymmetric Ring Opening of Epoxides with Amines -- 5.3 Copper-Catalyzed Asymmetric Ring Opening of Epoxides and Aziridines with Organometallic Reagents -- 5.3.1 Copper-Catalyzed Kinetic Resolution of Racemic Allylic Epoxides and Allylic Aziridines with Dialkylzincs -- 5.3.2 Copper-Catalyzed Enantioselective Desymmetrization of meso-Allylic Epoxides with Dialkylzincs.

5.3.3 Copper-Catalyzed Regiodivergent Kinetic Resolution of Racemic Allylic Epoxides with Dialkylzincs -- 5.3.4 Copper-Catalyzed Asymmetric Ring Opening of Racemic Strained Three-Membered Compounds with Organoaluminium and Grignard Reagents -- 5.4 Copper-Catalyzed Asymmetric Ring Opening of Heterobicyclic Systems with Organometallic Reagents -- 5.5 Conclusions -- References -- Chapter 6 Carbon-Boron and Carbon-Silicon Bond Formation -- 6.1 Introduction -- 6.2 C-B Bond Formation Reactions -- 6.2.1 Boron Reagents and Copper(I)-Boryl Species -- 6.2.2 Allylic C-B Couplings to Produce Allylboron Compounds and Related Reactions -- 6.2.3 â-Boration of á,â-Unsaturated Carbonyl Compounds -- 6.2.4 Hydroboration of Nonpolar Alkenes -- 6.3 C-Si Bond Formation Reactions -- 6.3.1 Allylic C-Si Coupling Producing Allylsilanes -- 6.3.2 β-Silylation of á,β-Unsaturated Carbonyl Compounds -- 6.4 Summary -- References -- Chapter 7 CuH in Asymmetric Reductions -- 7.1 Introduction -- 7.2 Asymmetric Conjugate Reductions -- 7.2.1 α,β-Unsaturated Sulfones -- 7.2.2 α,β-Unsaturated Nitriles and Nitroolefins -- 7.2.3 α,β-Unsaturated Ketones and Esters -- 7.3 Asymmetric 1,2-Additions -- 7.3.1 Aryl Ketones -- 7.3.2 Dialkyl Ketones -- 7.3.3 α,β-Unsaturated Ketones -- 7.4 Heterogeneous Catalysis -- 7.4.1 Charcoal -- 7.4.2 Nanocrystalline CuO -- 7.4.3 Cu-Al Hydrotalcite -- 7.4.4 Copper Ferrite Nanoparticles -- 7.5 Conclusions and Perspective -- References -- Chapter 8 Asymmetric Cyclopropanation and Aziridination Reactions -- 8.1 Introduction -- 8.2 Asymmetric Cyclopropanation -- 8.2.1 Intermolecular Cyclopropanation Using Metal Carbenes -- 8.2.1.1 Using Unsubstituted Copper Carbenes: Diazomethane -- 8.2.1.2 Using Copper Carbenes Bearing One Electron-Withdrawing Group.

8.2.1.3 Using Metal Carbenes Bearing Two Electron-Withdrawing Groups -- 8.2.1.4 Using Donor/Acceptor Copper Carbenes -- 8.2.2 Intramolecular Cyclopropanation Using Copper Carbenes -- 8.3 Asymmetric Aziridination -- 8.3.1 Intermolecular Aziridination Using Copper Nitrenes -- 8.3.1.1 Of Terminal Styrene Derivatives -- 8.3.1.2 Of â-Substituted Styrene Derivatives -- 8.3.1.3 Of Cyclic Styrene Derivatives -- 8.3.1.4 Of Cinnamate Derivatives -- 8.3.1.5 Of Chalcone Derivatives -- 8.3.1.6 Of Terminal Aliphatic Alkenes -- 8.3.2 Intramolecular Aziridination Using Copper Nitrenes -- 8.4 Conclusion -- References -- Chapter 9 Copper-Catalyzed Asymmetric Addition Reaction of Imines -- 9.1 Introduction -- 9.1.1 Asymmetric Alkylation of Imines with Organometallic Reagents -- 9.1.2 Possibility of Catalytic Reaction -- 9.2 Copper-Catalyzed Asymmetric Addition Reaction of Dialkylzinc to Imines -- 9.2.1 Addition to C=N Double Bonds of Imines -- 9.2.2 Conjugate Addition to α,β-Unsaturated Imines -- 9.3 Copper-Catalyzed Asymmetric Allylation, Arylation, and Alkynylation Reactions of Imines -- 9.3.1 Copper-Catalyzed Asymmetric Allylation of Imines -- 9.3.2 Copper-Catalyzed Asymmetric Arylation of Imines -- 9.3.3 Copper-Catalyzed Asymmetric Alkynylation of Imines -- 9.4 Copper as a Lewis Acid Catalyst for Asymmetric Reaction of Imines -- 9.4.1 Copper-Catalyzed Asymmetric Mannich-Type Reaction of Imines -- 9.4.2 Copper-Catalyzed Asymmetric Diels-Alder-type Reaction of Dienes with Imines -- 9.4.3 Copper-Catalyzed Asymmetric Henry Reaction of Imines -- 9.5 Conclusions -- References -- Chapter 10 Carbometallation Reactions -- 10.1 Introduction -- 10.2 Carbometallation of Cyclopropenes -- 10.2.1 Copper-Catalyzed Carbomagnesiation -- 10.2.2 Copper-Catalyzed Carbozincation -- 10.3 Carbometallation of Alkynes.

10.3.1 Copper-Catalyzed Carbometallation Followed by Zinc Homologation -- 10.3.2 Copper-Catalyzed Carbomagnesiation - Elimination Sequence -- 10.4 Summary -- Acknowledgments -- References -- Chapter 11 Chiral Copper Lewis Acids in Asymmetric Transformations -- 11.1 Introduction -- 11.2 Cycloadditions -- 11.2.1 Diels-Alder Cycloadditions -- 11.2.2 Hetero Diels-Alder Reactions -- 11.2.3 [3 + 2], [2 + 2], and [4 + 3] Cycloaddition Reactions -- 11.2.4 Nazarov Cyclization -- 11.3 Claisen Rearrangements -- 11.4 Ene Reactions -- 11.5 Nucleophilic Addition to C=O and C=N Double Bonds -- 11.5.1 Aldol Reactions -- 11.5.2 Mannich-Type Reactions -- 11.5.3 Nitroaldol/Nitro Mannich Reactions (Henry/Aza-Henry Reactions) -- 11.5.4 1,2-Addition-Type Friedel-Crafts Alkylation -- 11.6 Conjugate Additions -- 11.6.1 Mukaiyama Michael Reaction -- 11.6.2 Michael Addition to Enamides -- 11.6.3 Michael Addition of Carbon Nucleophiles -- 11.6.4 Aza-Michael Reaction -- 11.6.5 1,4-Addition-Type Friedel-Crafts Alkylation -- 11.7 α-Functionalization of Carbonyl Compounds -- 11.8 Kinetic Resolution -- 11.9 Asymmetric Desymmetrization -- 11.10 Free-Radical Reactions -- 11.11 Conclusions -- References -- Chapter 12 Mechanistic Aspects of Copper-Catalyzed Reactions -- 12.1 Introduction -- 12.2 Conjugate Addition -- 12.3 Allylic Alkylation and Substitution -- 12.4 Copper as Lewis Acid -- 12.5 1,2-Addition to Imines and Carbonyls -- 12.6 Copper Hydride -- 12.7 Cyclopropanation, Aziridination, and Allylic Oxidation -- References -- Chapter 13 NMR Spectroscopic Aspects -- 13.1 Introduction -- 13.2 Copper Complexes with Phosphoramidite Ligands -- 13.2.1 Precatalytic Copper Complexes -- 13.2.1.1 Structure Determination -- 13.2.1.2 Temperature Dependence -- 13.2.1.3 Ligand-Specific Aggregation Trends.

13.2.2 Phosphoramidite Trialkylaluminium Interactions.