Jian Zhou is a Professor of Chemistry in the Shanghai Key Laboratory of Green Chemistry and Chemical Processes at East China Normal University. He has broad experience in asymmetric catalysis and has published over 30 papers in leading scientific journals after his independent research. Dr. Zhou’s research focuses on the development of new chiral catalysts and catalytic asymmetric reactions for the efficient construction of fully substituted stereogenic carbon centres, as well as economical synthesis and novel tandem reactions.

• Preface xiContributors xiv1 Toward Ideal Asymmetric Catalysis 1Jian Zhou and Jin-Sheng Yu1.1 Introduction 11.2 Challenges to Realize Ideal Asymmetric Catalysis 71.3 Solutions 131.4 Borrow Ideas from Nature 221.5 Conclusion 32References 322 Multicatalyst System 37Zhong-Yan Cao Feng Zhu and Jian Zhou2.1 Introduction 372.2 Models of Substrate Activation 422.2.1 The Activation of Electrophiles 432.2.2 The Activation of Nucleophiles 542.2.3 SOMO Catalysis 642.3 Early Examples of the Application of Multicatalyst System in Asymmetric Catalysis 662.4 A General Introduction of Multicatalyst-Promoted Asymmetric Reactions 852.5 Classification of Multicatalyst-Promoted Asymmetric Reactions 952.6 Challenges and Possible Solutions 972.7 Multicatalyst System Versus Multifunctional Catalyst 1032.8 Multicatalyst System Versus Additives-Enhanced Catalysis 1052.9 Additive-Enhanced Catalysis 1072.9.1 Nitrogen-containing Organobase 1092.9.2 Inorganic Bases 1112.9.3 H2O 1142.9.4 Molecular Sieves and Dehydrators 1202.9.5 N-oxide P-oxide and As-oxide 1252.9.6 Alcohols and Phenols 1292.9.7 Ammonium Halides and Metal Halides 1332.9.8 Amides 1372.9.9 Brønsted Acids and Lewis Acids 1402.9.10 Two or More Additives Together 1442.10 Conclusion 147References 1483 Asymmetric Multifunctional Catalysis 159Jin-Sheng Yu and Jian Zhou3.1 Introduction 1593.2 Asymmetric Multifunctional Organocatalysis 1643.2.1 H-Bond Donor–Tertiary Amine Catalysis 1653.2.2 H-Bond Donor–Enamine Catalysis 1933.2.3 H-Bond Donor–Phase Transfer Catalysis 2033.2.4 H-Bond Donor–Tertiary Phosphine Catalysis 2093.2.5 Chiral Phosphoric Acid Catalysis 2143.2.6 Asymmetric Bifunctional Salt Catalysis 2173.2.7 Miscellaneous 2223.3 Asymmetric Hybrid Organo/Metal Catalysis 2273.3.1 Brønsted Base/Lewis Acid Bifunctional Catalysis 2283.3.2 Lewis Base/Lewis Acid Bifunctional Catalysis 2333.3.3 Brønsted Acid/Lewis Acid Bifunctional Catalysis 2363.3.4 Enamine/Lewis Acid Bifunctional Catalysis 2383.3.5 Hemilable Trisoxazolines 2403.4 Asymmetric Multifunctional Multimetallic Catalysis 2423.4.1 Asymmetric Multifunctional Heteromultimetallic Catalysis 2433.4.2 Asymmetric Multifunctional Homomultimetallic Catalysis 2513.5 Anion-Enabled Bifunctional Asymmetric Catalysis 2593.5.1 Ammonium Fluorides or Metal Fluorides 2623.5.2 Metal Phosphates 2653.5.3 Metal Carboxylates 2653.5.4 Ammonium or Metal Aryloxides 2693.5.5 Hydroxides and Alkoxides 2713.5.6 Metal Amides 2763.6 Conclusion 277References 2774 Asymmetric Cooperative Catalysis 291Long Chen Yun-Lin Liu and Jian Zhou4.1 Introduction 2914.2 Catalytic Asymmetric Michael Addition Reaction 2924.2.1 Combining Multiple Metal Catalysts 2924.2.2 Combining Two Distinct Organocatalysts 2934.2.3 Combining Metal Catalyst with Organocatalyst 2974.3 Catalytic Asymmetric Mannich Reaction 2994.3.1 Combining Lewis Acid Catalyst and Brønsted Base Catalyst 3004.3.2 Combining Brønsted Acid Catalyst and Lewis Acid Catalyst 3014.3.3 Combining Brønsted Acid Catalyst and Secondary Amine Catalyst 3034.4 Catalytic Asymmetric Conia-Ene Reaction 3044.4.1 Combining Chiral Lewis Acid and Achiral Lewis Acid 3044.4.2 Combining Chiral Brønsted Base and Achiral Lewis Acid 3064.5 Catalytic Asymmetric Umpolung Reaction 3074.5.1 Combining NHC Catalyst and Lewis Acid Catalyst 3074.5.2 Combining NHC Catalyst and Brønsted Acid Catalyst 3134.6 Catalytic Asymmetric Cyanosilylation Reaction 3154.7 α-Alkylation Reaction of Carbonyl Compounds 3174.7.1 α-Alkylation of Carbonyl Compounds using Alcohols as Alkylation Reagents 3174.7.2 α-Alkylation of Carbonyl Compounds through Benzylic C H Bond Oxidation 3254.8 Catalytic Asymmetric Allylic Alkylation Reaction 3264.8.1 Combining Achiral Transition Metal with Chiral LUMO-Lowering Catalysis 3274.8.2 Combining Chiral Transition Metal Catalysis with Achiral Organocatalyst 3314.9 Catalytic Asymmetric Aldol-Type Reaction 3354.10 Catalytic Asymmetric (Aza)-Morita–Baylis–Hillman Reaction 3384.10.1 Chiral Lewis Base/Achiral Acid Cocatalyzed (aza)-MBH Reaction 3414.10.2 Achiral Lewis Base/Chiral Acid Cocatalyzed (aza)-MBH Reaction 3424.11 Catalytic Asymmetric Hydrogenation Reaction 3464.12 Catalytic Asymmetric Cycloaddition Reaction 3504.12.1 [2 + 2] Reaction 3514.12.2 [4 + 2] Reaction 3524.13 Catalytic Asymmetric N H Insertion Reaction 3564.14 Catalytic Asymmetric α-Functionalization of Aldehydes 3584.15 Miscellaneous Reaction 3604.16 Conclusion 364References 3655 Asymmetric Double Activation Catalysis by Multicatalyst System 373Long Chen Zhong-Yan Cao and Jian Zhou5.1 Introduction 3735.2 Double Activation by Aminocatalysis and Lewis Base Catalysis 3745.3 Asymmetric Double Primary Amine and Brønsted Acid Catalysis 3785.3.1 Diels–Alder (DA)Reaction 3795.3.2 Michael Addition 3795.3.3 Epoxidation 3865.3.4 Miscellaneous Reaction 3905.4 Asymmetric Double Metal and Brønsted Base Catalysis 391 5.4.1 [3 + 2] Cycloaddition 3925.4.2 Aldol Reaction 3965.4.3 Miscellaneous Reactions 3995.5 Asymmetric H-Bond Donor Catalysis and Lewis Base Catalysis 4015.6 Sequential Double Activation Catalysis 4045.7 Conclusion 408References 4086 Asymmetric Assisted Catalysis by Multicatalyst System 411Xing-Ping Zeng and Jian Zhou6.1 Introduction 4116.2 Asymmetric Assisted Catalysis within Acids and Bases 4146.2.1 Acid Assisted Acid Catalysis 4156.2.2 Base Assisted Brønsted Acid Catalysis 4336.2.3 Lewis Base Assisted Brønsted Base Catalysis 4356.2.4 Acid Assisted Base Catalysis 4376.2.5 Miscellaneous 4396.3 Modulation of a Metal Complex by a Chiral Ligand 4436.3.1 Modulation of a Chiral Metal Complex with a Chiral Ligand 4446.3.2 Asymmetric Deactivation Activation and Deactivation/Activation 4516.3.3 Asymmetric Activation of Racemic Catalysts Bearing Tropos Ligand 4606.4 Supramolecular-Type Assisted Catalysis 4626.5 Conclusion 469References 4697 Asymmetric Catalysis Facilitated by Photochemical or Electrochemical Methods 475Zhong-Yan Cao and Jian Zhou7.1 Introduction 4757.2 Catalytic Asymmetric Reaction Facilitated by Photochemical Method 4767.2.1 Asymmetric Oxidation Reactions 4777.2.2 α-Functionalization of Tertiary Amines 4797.2.3 α-Functionalization of Aldehydes 4827.2.4 [2 + 2] Photocycloaddition Reaction 4887.2.5 Miscellaneous Reactions 4897.3 Catalytic Asymmetric Reactions Facilitated by Electrochemical Method 4937.4 Conclusion 497References 4988 Multicatalyst System Realized Asymmetric Tandem Reactions 501Feng Zhou Yun-Lin Liu and Jian Zhou8.1 Introduction 5018.1.1 Basic Models of MSRATR 5028.1.2 Challenges and Solutions for the Development of MSRATR 5078.2 Multicatalyst Systems of Homocombination 5098.2.1 By Multiple Metal Catalysts 5098.2.2 By Multiple Organocatalysts 5228.2.3 By Multiple Enzymes 5588.3 Hetero Combination System Realized MSRATR 5668.3.1 By Combination of Metal and Organocatalysts 5668.3.2 By Combination of Metal Catalysis and Biocatalysis 6048.3.3 By Combination of Organocatalysis and Biocatalysis 6208.4 Conclusion 622References 6239 Waste-Mediated Reactions 633Jian Zhou and Xing-Ping Zeng9.1 Introduction 6339.2 Historical Background 6369.3 Waste-Promoted Single Reactions 6379.3.1 Waste Act as a Brønsted Base 6389.3.2 By-product as Lewis Base 6499.4 By-Products as Acidic Promoter 6539.5 Waste-Promoted Tandem Reactions 6549.6 Waste-Catalyzed Tandem Reactions 6579.7 Conclusions 666References 66710 Multicatalyst System Mediated Asymmetric Reactions in Total Synthesis 671Yun-Lin Liu and Jian Zhou10.1 Introduction 67110.2 Application of Multicatalyst System Mediated Single Reactions 67210.3 Application of Multicatalyst Mediated Tandem Reaction 67710.4 Conclusion 685References 686Index 689

Jian Zhou is a Professor of Chemistry in the Shanghai Key Laboratory of Green Chemistry and Chemical Processes at East China Normal University. He has broad experience in asymmetric catalysis and has published over 30 papers in leading scientific journals after his independent research. Dr. Zhou’s research focuses on the development of new chiral catalysts and catalytic asymmetric reactions for the efficient construction of fully substituted stereogenic carbon centres, as well as economical synthesis and novel tandem reactions.

• Preface xiContributors xiv1 Toward Ideal Asymmetric Catalysis 1Jian Zhou and Jin-Sheng Yu1.1 Introduction 11.2 Challenges to Realize Ideal Asymmetric Catalysis 71.3 Solutions 131.4 Borrow Ideas from Nature 221.5 Conclusion 32References 322 Multicatalyst System 37Zhong-Yan Cao Feng Zhu and Jian Zhou2.1 Introduction 372.2 Models of Substrate Activation 422.2.1 The Activation of Electrophiles 432.2.2 The Activation of Nucleophiles 542.2.3 SOMO Catalysis 642.3 Early Examples of the Application of Multicatalyst System in Asymmetric Catalysis 662.4 A General Introduction of Multicatalyst-Promoted Asymmetric Reactions 852.5 Classification of Multicatalyst-Promoted Asymmetric Reactions 952.6 Challenges and Possible Solutions 972.7 Multicatalyst System Versus Multifunctional Catalyst 1032.8 Multicatalyst System Versus Additives-Enhanced Catalysis 1052.9 Additive-Enhanced Catalysis 1072.9.1 Nitrogen-containing Organobase 1092.9.2 Inorganic Bases 1112.9.3 H2O 1142.9.4 Molecular Sieves and Dehydrators 1202.9.5 N-oxide P-oxide and As-oxide 1252.9.6 Alcohols and Phenols 1292.9.7 Ammonium Halides and Metal Halides 1332.9.8 Amides 1372.9.9 Brønsted Acids and Lewis Acids 1402.9.10 Two or More Additives Together 1442.10 Conclusion 147References 1483 Asymmetric Multifunctional Catalysis 159Jin-Sheng Yu and Jian Zhou3.1 Introduction 1593.2 Asymmetric Multifunctional Organocatalysis 1643.2.1 H-Bond Donor–Tertiary Amine Catalysis 1653.2.2 H-Bond Donor–Enamine Catalysis 1933.2.3 H-Bond Donor–Phase Transfer Catalysis 2033.2.4 H-Bond Donor–Tertiary Phosphine Catalysis 2093.2.5 Chiral Phosphoric Acid Catalysis 2143.2.6 Asymmetric Bifunctional Salt Catalysis 2173.2.7 Miscellaneous 2223.3 Asymmetric Hybrid Organo/Metal Catalysis 2273.3.1 Brønsted Base/Lewis Acid Bifunctional Catalysis 2283.3.2 Lewis Base/Lewis Acid Bifunctional Catalysis 2333.3.3 Brønsted Acid/Lewis Acid Bifunctional Catalysis 2363.3.4 Enamine/Lewis Acid Bifunctional Catalysis 2383.3.5 Hemilable Trisoxazolines 2403.4 Asymmetric Multifunctional Multimetallic Catalysis 2423.4.1 Asymmetric Multifunctional Heteromultimetallic Catalysis 2433.4.2 Asymmetric Multifunctional Homomultimetallic Catalysis 2513.5 Anion-Enabled Bifunctional Asymmetric Catalysis 2593.5.1 Ammonium Fluorides or Metal Fluorides 2623.5.2 Metal Phosphates 2653.5.3 Metal Carboxylates 2653.5.4 Ammonium or Metal Aryloxides 2693.5.5 Hydroxides and Alkoxides 2713.5.6 Metal Amides 2763.6 Conclusion 277References 2774 Asymmetric Cooperative Catalysis 291Long Chen Yun-Lin Liu and Jian Zhou4.1 Introduction 2914.2 Catalytic Asymmetric Michael Addition Reaction 2924.2.1 Combining Multiple Metal Catalysts 2924.2.2 Combining Two Distinct Organocatalysts 2934.2.3 Combining Metal Catalyst with Organocatalyst 2974.3 Catalytic Asymmetric Mannich Reaction 2994.3.1 Combining Lewis Acid Catalyst and Brønsted Base Catalyst 3004.3.2 Combining Brønsted Acid Catalyst and Lewis Acid Catalyst 3014.3.3 Combining Brønsted Acid Catalyst and Secondary Amine Catalyst 3034.4 Catalytic Asymmetric Conia-Ene Reaction 3044.4.1 Combining Chiral Lewis Acid and Achiral Lewis Acid 3044.4.2 Combining Chiral Brønsted Base and Achiral Lewis Acid 3064.5 Catalytic Asymmetric Umpolung Reaction 3074.5.1 Combining NHC Catalyst and Lewis Acid Catalyst 3074.5.2 Combining NHC Catalyst and Brønsted Acid Catalyst 3134.6 Catalytic Asymmetric Cyanosilylation Reaction 3154.7 α-Alkylation Reaction of Carbonyl Compounds 3174.7.1 α-Alkylation of Carbonyl Compounds using Alcohols as Alkylation Reagents 3174.7.2 α-Alkylation of Carbonyl Compounds through Benzylic C H Bond Oxidation 3254.8 Catalytic Asymmetric Allylic Alkylation Reaction 3264.8.1 Combining Achiral Transition Metal with Chiral LUMO-Lowering Catalysis 3274.8.2 Combining Chiral Transition Metal Catalysis with Achiral Organocatalyst 3314.9 Catalytic Asymmetric Aldol-Type Reaction 3354.10 Catalytic Asymmetric (Aza)-Morita–Baylis–Hillman Reaction 3384.10.1 Chiral Lewis Base/Achiral Acid Cocatalyzed (aza)-MBH Reaction 3414.10.2 Achiral Lewis Base/Chiral Acid Cocatalyzed (aza)-MBH Reaction 3424.11 Catalytic Asymmetric Hydrogenation Reaction 3464.12 Catalytic Asymmetric Cycloaddition Reaction 3504.12.1 [2 + 2] Reaction 3514.12.2 [4 + 2] Reaction 3524.13 Catalytic Asymmetric N H Insertion Reaction 3564.14 Catalytic Asymmetric α-Functionalization of Aldehydes 3584.15 Miscellaneous Reaction 3604.16 Conclusion 364References 3655 Asymmetric Double Activation Catalysis by Multicatalyst System 373Long Chen Zhong-Yan Cao and Jian Zhou5.1 Introduction 3735.2 Double Activation by Aminocatalysis and Lewis Base Catalysis 3745.3 Asymmetric Double Primary Amine and Brønsted Acid Catalysis 3785.3.1 Diels–Alder (DA)Reaction 3795.3.2 Michael Addition 3795.3.3 Epoxidation 3865.3.4 Miscellaneous Reaction 3905.4 Asymmetric Double Metal and Brønsted Base Catalysis 391 5.4.1 [3 + 2] Cycloaddition 3925.4.2 Aldol Reaction 3965.4.3 Miscellaneous Reactions 3995.5 Asymmetric H-Bond Donor Catalysis and Lewis Base Catalysis 4015.6 Sequential Double Activation Catalysis 4045.7 Conclusion 408References 4086 Asymmetric Assisted Catalysis by Multicatalyst System 411Xing-Ping Zeng and Jian Zhou6.1 Introduction 4116.2 Asymmetric Assisted Catalysis within Acids and Bases 4146.2.1 Acid Assisted Acid Catalysis 4156.2.2 Base Assisted Brønsted Acid Catalysis 4336.2.3 Lewis Base Assisted Brønsted Base Catalysis 4356.2.4 Acid Assisted Base Catalysis 4376.2.5 Miscellaneous 4396.3 Modulation of a Metal Complex by a Chiral Ligand 4436.3.1 Modulation of a Chiral Metal Complex with a Chiral Ligand 4446.3.2 Asymmetric Deactivation Activation and Deactivation/Activation 4516.3.3 Asymmetric Activation of Racemic Catalysts Bearing Tropos Ligand 4606.4 Supramolecular-Type Assisted Catalysis 4626.5 Conclusion 469References 4697 Asymmetric Catalysis Facilitated by Photochemical or Electrochemical Methods 475Zhong-Yan Cao and Jian Zhou7.1 Introduction 4757.2 Catalytic Asymmetric Reaction Facilitated by Photochemical Method 4767.2.1 Asymmetric Oxidation Reactions 4777.2.2 α-Functionalization of Tertiary Amines 4797.2.3 α-Functionalization of Aldehydes 4827.2.4 [2 + 2] Photocycloaddition Reaction 4887.2.5 Miscellaneous Reactions 4897.3 Catalytic Asymmetric Reactions Facilitated by Electrochemical Method 4937.4 Conclusion 497References 4988 Multicatalyst System Realized Asymmetric Tandem Reactions 501Feng Zhou Yun-Lin Liu and Jian Zhou8.1 Introduction 5018.1.1 Basic Models of MSRATR 5028.1.2 Challenges and Solutions for the Development of MSRATR 5078.2 Multicatalyst Systems of Homocombination 5098.2.1 By Multiple Metal Catalysts 5098.2.2 By Multiple Organocatalysts 5228.2.3 By Multiple Enzymes 5588.3 Hetero Combination System Realized MSRATR 5668.3.1 By Combination of Metal and Organocatalysts 5668.3.2 By Combination of Metal Catalysis and Biocatalysis 6048.3.3 By Combination of Organocatalysis and Biocatalysis 6208.4 Conclusion 622References 6239 Waste-Mediated Reactions 633Jian Zhou and Xing-Ping Zeng9.1 Introduction 6339.2 Historical Background 6369.3 Waste-Promoted Single Reactions 6379.3.1 Waste Act as a Brønsted Base 6389.3.2 By-product as Lewis Base 6499.4 By-Products as Acidic Promoter 6539.5 Waste-Promoted Tandem Reactions 6549.6 Waste-Catalyzed Tandem Reactions 6579.7 Conclusions 666References 66710 Multicatalyst System Mediated Asymmetric Reactions in Total Synthesis 671Yun-Lin Liu and Jian Zhou10.1 Introduction 67110.2 Application of Multicatalyst System Mediated Single Reactions 67210.3 Application of Multicatalyst Mediated Tandem Reaction 67710.4 Conclusion 685References 686Index 689

Jian Zhou is a Professor of Chemistry in the Shanghai Key Laboratory of Green Chemistry and Chemical Processes at East China Normal University. He has broad experience in asymmetric catalysis and has published over 30 papers in leading scientific journals after his independent research. Dr. Zhou’s research focuses on the development of new chiral catalysts and catalytic asymmetric reactions for the efficient construction of fully substituted stereogenic carbon centres, as well as economical synthesis and novel tandem reactions.

• Preface xiContributors xiv1 Toward Ideal Asymmetric Catalysis 1Jian Zhou and Jin-Sheng Yu1.1 Introduction 11.2 Challenges to Realize Ideal Asymmetric Catalysis 71.3 Solutions 131.4 Borrow Ideas from Nature 221.5 Conclusion 32References 322 Multicatalyst System 37Zhong-Yan Cao Feng Zhu and Jian Zhou2.1 Introduction 372.2 Models of Substrate Activation 422.2.1 The Activation of Electrophiles 432.2.2 The Activation of Nucleophiles 542.2.3 SOMO Catalysis 642.3 Early Examples of the Application of Multicatalyst System in Asymmetric Catalysis 662.4 A General Introduction of Multicatalyst-Promoted Asymmetric Reactions 852.5 Classification of Multicatalyst-Promoted Asymmetric Reactions 952.6 Challenges and Possible Solutions 972.7 Multicatalyst System Versus Multifunctional Catalyst 1032.8 Multicatalyst System Versus Additives-Enhanced Catalysis 1052.9 Additive-Enhanced Catalysis 1072.9.1 Nitrogen-containing Organobase 1092.9.2 Inorganic Bases 1112.9.3 H2O 1142.9.4 Molecular Sieves and Dehydrators 1202.9.5 N-oxide P-oxide and As-oxide 1252.9.6 Alcohols and Phenols 1292.9.7 Ammonium Halides and Metal Halides 1332.9.8 Amides 1372.9.9 Brønsted Acids and Lewis Acids 1402.9.10 Two or More Additives Together 1442.10 Conclusion 147References 1483 Asymmetric Multifunctional Catalysis 159Jin-Sheng Yu and Jian Zhou3.1 Introduction 1593.2 Asymmetric Multifunctional Organocatalysis 1643.2.1 H-Bond Donor–Tertiary Amine Catalysis 1653.2.2 H-Bond Donor–Enamine Catalysis 1933.2.3 H-Bond Donor–Phase Transfer Catalysis 2033.2.4 H-Bond Donor–Tertiary Phosphine Catalysis 2093.2.5 Chiral Phosphoric Acid Catalysis 2143.2.6 Asymmetric Bifunctional Salt Catalysis 2173.2.7 Miscellaneous 2223.3 Asymmetric Hybrid Organo/Metal Catalysis 2273.3.1 Brønsted Base/Lewis Acid Bifunctional Catalysis 2283.3.2 Lewis Base/Lewis Acid Bifunctional Catalysis 2333.3.3 Brønsted Acid/Lewis Acid Bifunctional Catalysis 2363.3.4 Enamine/Lewis Acid Bifunctional Catalysis 2383.3.5 Hemilable Trisoxazolines 2403.4 Asymmetric Multifunctional Multimetallic Catalysis 2423.4.1 Asymmetric Multifunctional Heteromultimetallic Catalysis 2433.4.2 Asymmetric Multifunctional Homomultimetallic Catalysis 2513.5 Anion-Enabled Bifunctional Asymmetric Catalysis 2593.5.1 Ammonium Fluorides or Metal Fluorides 2623.5.2 Metal Phosphates 2653.5.3 Metal Carboxylates 2653.5.4 Ammonium or Metal Aryloxides 2693.5.5 Hydroxides and Alkoxides 2713.5.6 Metal Amides 2763.6 Conclusion 277References 2774 Asymmetric Cooperative Catalysis 291Long Chen Yun-Lin Liu and Jian Zhou4.1 Introduction 2914.2 Catalytic Asymmetric Michael Addition Reaction 2924.2.1 Combining Multiple Metal Catalysts 2924.2.2 Combining Two Distinct Organocatalysts 2934.2.3 Combining Metal Catalyst with Organocatalyst 2974.3 Catalytic Asymmetric Mannich Reaction 2994.3.1 Combining Lewis Acid Catalyst and Brønsted Base Catalyst 3004.3.2 Combining Brønsted Acid Catalyst and Lewis Acid Catalyst 3014.3.3 Combining Brønsted Acid Catalyst and Secondary Amine Catalyst 3034.4 Catalytic Asymmetric Conia-Ene Reaction 3044.4.1 Combining Chiral Lewis Acid and Achiral Lewis Acid 3044.4.2 Combining Chiral Brønsted Base and Achiral Lewis Acid 3064.5 Catalytic Asymmetric Umpolung Reaction 3074.5.1 Combining NHC Catalyst and Lewis Acid Catalyst 3074.5.2 Combining NHC Catalyst and Brønsted Acid Catalyst 3134.6 Catalytic Asymmetric Cyanosilylation Reaction 3154.7 α-Alkylation Reaction of Carbonyl Compounds 3174.7.1 α-Alkylation of Carbonyl Compounds using Alcohols as Alkylation Reagents 3174.7.2 α-Alkylation of Carbonyl Compounds through Benzylic C H Bond Oxidation 3254.8 Catalytic Asymmetric Allylic Alkylation Reaction 3264.8.1 Combining Achiral Transition Metal with Chiral LUMO-Lowering Catalysis 3274.8.2 Combining Chiral Transition Metal Catalysis with Achiral Organocatalyst 3314.9 Catalytic Asymmetric Aldol-Type Reaction 3354.10 Catalytic Asymmetric (Aza)-Morita–Baylis–Hillman Reaction 3384.10.1 Chiral Lewis Base/Achiral Acid Cocatalyzed (aza)-MBH Reaction 3414.10.2 Achiral Lewis Base/Chiral Acid Cocatalyzed (aza)-MBH Reaction 3424.11 Catalytic Asymmetric Hydrogenation Reaction 3464.12 Catalytic Asymmetric Cycloaddition Reaction 3504.12.1 [2 + 2] Reaction 3514.12.2 [4 + 2] Reaction 3524.13 Catalytic Asymmetric N H Insertion Reaction 3564.14 Catalytic Asymmetric α-Functionalization of Aldehydes 3584.15 Miscellaneous Reaction 3604.16 Conclusion 364References 3655 Asymmetric Double Activation Catalysis by Multicatalyst System 373Long Chen Zhong-Yan Cao and Jian Zhou5.1 Introduction 3735.2 Double Activation by Aminocatalysis and Lewis Base Catalysis 3745.3 Asymmetric Double Primary Amine and Brønsted Acid Catalysis 3785.3.1 Diels–Alder (DA)Reaction 3795.3.2 Michael Addition 3795.3.3 Epoxidation 3865.3.4 Miscellaneous Reaction 3905.4 Asymmetric Double Metal and Brønsted Base Catalysis 391 5.4.1 [3 + 2] Cycloaddition 3925.4.2 Aldol Reaction 3965.4.3 Miscellaneous Reactions 3995.5 Asymmetric H-Bond Donor Catalysis and Lewis Base Catalysis 4015.6 Sequential Double Activation Catalysis 4045.7 Conclusion 408References 4086 Asymmetric Assisted Catalysis by Multicatalyst System 411Xing-Ping Zeng and Jian Zhou6.1 Introduction 4116.2 Asymmetric Assisted Catalysis within Acids and Bases 4146.2.1 Acid Assisted Acid Catalysis 4156.2.2 Base Assisted Brønsted Acid Catalysis 4336.2.3 Lewis Base Assisted Brønsted Base Catalysis 4356.2.4 Acid Assisted Base Catalysis 4376.2.5 Miscellaneous 4396.3 Modulation of a Metal Complex by a Chiral Ligand 4436.3.1 Modulation of a Chiral Metal Complex with a Chiral Ligand 4446.3.2 Asymmetric Deactivation Activation and Deactivation/Activation 4516.3.3 Asymmetric Activation of Racemic Catalysts Bearing Tropos Ligand 4606.4 Supramolecular-Type Assisted Catalysis 4626.5 Conclusion 469References 4697 Asymmetric Catalysis Facilitated by Photochemical or Electrochemical Methods 475Zhong-Yan Cao and Jian Zhou7.1 Introduction 4757.2 Catalytic Asymmetric Reaction Facilitated by Photochemical Method 4767.2.1 Asymmetric Oxidation Reactions 4777.2.2 α-Functionalization of Tertiary Amines 4797.2.3 α-Functionalization of Aldehydes 4827.2.4 [2 + 2] Photocycloaddition Reaction 4887.2.5 Miscellaneous Reactions 4897.3 Catalytic Asymmetric Reactions Facilitated by Electrochemical Method 4937.4 Conclusion 497References 4988 Multicatalyst System Realized Asymmetric Tandem Reactions 501Feng Zhou Yun-Lin Liu and Jian Zhou8.1 Introduction 5018.1.1 Basic Models of MSRATR 5028.1.2 Challenges and Solutions for the Development of MSRATR 5078.2 Multicatalyst Systems of Homocombination 5098.2.1 By Multiple Metal Catalysts 5098.2.2 By Multiple Organocatalysts 5228.2.3 By Multiple Enzymes 5588.3 Hetero Combination System Realized MSRATR 5668.3.1 By Combination of Metal and Organocatalysts 5668.3.2 By Combination of Metal Catalysis and Biocatalysis 6048.3.3 By Combination of Organocatalysis and Biocatalysis 6208.4 Conclusion 622References 6239 Waste-Mediated Reactions 633Jian Zhou and Xing-Ping Zeng9.1 Introduction 6339.2 Historical Background 6369.3 Waste-Promoted Single Reactions 6379.3.1 Waste Act as a Brønsted Base 6389.3.2 By-product as Lewis Base 6499.4 By-Products as Acidic Promoter 6539.5 Waste-Promoted Tandem Reactions 6549.6 Waste-Catalyzed Tandem Reactions 6579.7 Conclusions 666References 66710 Multicatalyst System Mediated Asymmetric Reactions in Total Synthesis 671Yun-Lin Liu and Jian Zhou10.1 Introduction 67110.2 Application of Multicatalyst System Mediated Single Reactions 67210.3 Application of Multicatalyst Mediated Tandem Reaction 67710.4 Conclusion 685References 686Index 689