Asymmetric Organo-Metal Catalysis

Liu-Zhu Gong, PhD, is Professor of Organic Chemistry at the University of Science and Technology of China. He received his doctorate from the Institute of Chemistry, Chinese Academy of Sciences, in 2000. His research focuses on asymmetric organocatalysis combined with metal catalysis, asymmetric organocatalysis, and the total synthesis of natural products.

• Preface ix1 Why Is Organo/Metal Combined Catalysis Necessary? 11.1 Introduction 11.2 Early Stage of Organo/Metal Combined Catalysis and General Principles 31.3 Organo/Metal Cooperative Catalysis 71.3.1 Control of Stereochemistry 71.3.2 Cooperative Activation of Chemical Bonds 91.4 Organo/Metal Relay and Sequential Catalysis 111.5 Conclusion 16References 162 Metal/Phase-Transfer Catalyst Combined Catalysis 192.1 Introduction 192.1.1 Early Racemic Examples: PTC and Transition Metal Co-catalyzed Reactions 192.2 Asymmetric Metal/Phase-Transfer Catalyst Combined Catalysis 202.2.1 Combination of Cationic PTC and Transition Metal in Asymmetric Catalysis 222.2.2 Combination of Anionic PTC and Transition Metal in Asymmetric Catalysis 292.3 Conclusion 33References 343 Enamine-Metal Combined Catalysis 393.1 Introduction: Combined Enamine Activation and Metal Catalysis 393.2 Catalytic Asymmetric α-Allylation of Carbonyls 393.2.1 Oxidative Addition-Initiated Allylic Alkylation 393.2.2 Metal Hydride-Initiated Allylic Alkylation 483.2.3 Lewis Acid-Mediated SN1 or SN2 Reaction 503.3 Catalytic Asymmetric Substitution 513.4 Catalytic Asymmetric α-Alkenylation, α-Arylation, and α-Trifluoromethylation of Carbonyl Compounds 553.5 Asymmetric Addition to Alkynes by Cooperative Catalysis with π-Lewis Acids 593.6 Catalytic Asymmetric Propargylic Substitution Reaction of Carbonyl Compounds 613.7 Catalytic Asymmetric α-Oxidation of Aldehydes 633.8 Relay Catalysis 643.8.1 Catalytic Asymmetric Cross Dehydrogenative Coupling 643.8.2 Transformation of Olefins 683.9 Conclusion 70References 714 Iminium and Metal Combined Catalysis 754.1 Introduction: Iminium Activation and Metal Combined Catalysis 754.2 Iminium Activation and Palladium Catalysis 764.2.1 Enantioselective Conjugate Addition Reaction 764.2.2 Asymmetric [3+2] Cycloaddition Via Ring-Opening Oxidative Addition 774.2.3 Asymmetric Michael Addition and Carbocyclization Cascade 814.2.4 Asymmetric Oxidative Cascade Reaction 834.3 Iminium Activation and Coinage Metal Catalysis 834.4 Iminium Activation and Other Metal Catalysis 854.5 Conclusion 87References 885 Brønsted Acid and Transition Metal Cooperative Catalysis 915.1 Introduction 915.2 Early Stage of Metal/Brønsted Acid Cooperative Catalysis 935.3 Metal Alkynylide-Mediated Transformations 935.4 π-Allyl-Metal-Mediated Transformation 955.5 Asymmetric Hydrogenation of C—N Double Bond 1075.6 Metal Carbene-Mediated Transformations 1105.7 π-Lewis Acid Mediated Transformations 1165.8 Summary and Outlook 119References 1206 Metal-Brønsted Acid Relay Catalysis 1256.1 Introduction 1256.2 π-Lewis Acid-Chiral Brønsted Acid Relay Catalysis 1256.2.1 Hydroamination-Initiated Cascade Reaction 1276.2.2 Hydroalkoxylation Mediated Relay Catalysis 1326.2.3 Hydrosiloxylation Mediated Relay Catalysis 1366.2.4 Relay Catalysis Involving the Addition of Nitrone or Nitro Group to Alkynes 1386.2.5 Relay Catalysis Involving the Addition of Carbon Nucleophiles to Alkynes 1396.3 Metal/Brønsted Acid Relay Catalysis Involving Alkene Metathesis 1416.4 Metal/Brønsted Acid Relay Catalysis Involving Alkene Isomerization 1446.5 Metal/Brønsted Acid Relay Catalysis Involving Hydrogenation 1516.6 Palladium/Brønsted Acid Relay Catalytic Asymmetric Allylation of Carbonyls 1556.7 Metal/Brønsted Acid Relay Catalysis Involving Hydroformylation 1576.8 Metal/Brønsted Acid Relay Catalysis Involving Metal Carbene Formation 1606.8.1 Cascade Metal Carbene Formation and Asymmetric Protonation 1606.8.2 Multiple Cascade Reaction Initiated with Metal Carbene 1656.9 Lewis Acid/Chiral Brønsted Acid Relay Catalysis 1676.10 Miscellaneous 1696.11 Summary and Outlook 172References 1737 Lewis Base–Lewis Acid Cooperative Catalysis 1797.1 Introduction: Combined Lewis Base and Lewis Acid Activations 1797.1.1 Early Examples in Lewis Base–Lewis Acid Cooperative Catalysis 1837.2 Asymmetric Reactions Driven by Tertiary Amine-Mediated Ammonium Enolates 1847.2.1 Asymmetric Baylis–Hillman Reactions 1847.2.2 Asymmetric [2+2] Reactions 1867.2.3 Asymmetric [4+2] Reactions 1927.2.4 Asymmetric α-Functionalization of Carbonyl Compounds 1967.3 Asymmetric Reactions Driven by NHC-Mediated Homoenolates 1987.3.1 Asymmetric Annulation Reactions 2017.3.2 Asymmetric β-Protonation Reactions 2117.3.3 Asymmetric Kinetic Resolutions 2157.4 Asymmetric Reactions Driven by NHC-Mediated Azolium Enolates 2167.5 Asymmetric Reactions Driven by Ammonium Salts 2217.6 Asymmetric Reactions Driven by NHC-Mediated α,β-Unsaturated Acyl Azoliums 2257.6.1 Asymmetric [3+3] Reactions 2257.6.2 Asymmetric Cascade Reactions 2297.6.3 Asymmetric Kinetic Resolutions 2317.7 Conclusion 235References 2358 Lewis Base-Transition Metal Cooperative Catalysis 2418.1 Introduction 2418.2 Phosphine and Transition Metal Cooperative Catalysis 2438.3 N-Heterocyclic Carbene and Transition Metal Cooperative Catalysis 2448.3.1 π-Allyl Metal Mediated Transformations 2458.3.2 Alkynyl-metal Mediated Transformations 2538.3.3 Metal-allenylidene Mediated Transformations 2548.4 Tertiary Amine and Transition Metal Cooperative Catalysis 2588.4.1 π-Allyl Metal Mediated Transformations 2588.4.2 π-Benzyl-metal Mediated Transformations 2638.4.3 Metal-allenylidene Mediated Transformations 2658.4.4 Other Transition Metal Mediated Transformations 2678.5 Conclusions 271References 2719 Chiral Organocatalyst Combined with Transition Metal Based Photoredox Catalyst 2779.1 Introduction 2779.2 Covalent-Based Organocatalytic Activation in Combination with Transition Metal-Based Photoredox Catalyst 2799.2.1 Chiral Amine/Photoredox Combined Catalysis 2799.3 Photoredox-Mediated SOMO Catalysis 2849.4 Nucleophilic Organocatalyst in Combination with Photoredox Catalyst 2889.5 Noncovalent-Based Organocatalytic Activation in Combination with Transition Metal-Based Photoredox Catalyst 2909.5.1 Chiral Phosphate/Photoredox Combined Catalysis 2909.6 Asymmetric Ion-Pair/Photoredox Combined Catalysis 2959.7 Summary and Outlook 297References 29710 Applications in Organic Synthesis 30110.1 Introduction 30110.2 Applications of Chiral Phosphoric Acid-Metal Cooperative Catalysis 30110.3 Application of Transition Metal Catalysis Combined with Secondary Amine Catalysis 30510.4 Application of Photocatalysis Combined with Organocatalysis 31010.5 Application of Lewis Base–Lewis Acid Cooperative Catalysis 31210.6 Application of Lewis Base–Transition Metal Relay Catalysis 31610.7 Application of Metal-Brønsted Acid Relay Catalysis 31610.8 Conclusion 320References 320Index 325