Cooperative Catalysis -- Contents -- Preface -- Acknowledgments -- List of Contributors -- Chapter 1 Lewis Acid-Bronsted Base Catalysis -- 1.1 Introduction -- 1.2 Lewis Acid-Bronsted Base Catalysis in Metalloenzymes -- 1.3 Hard Lewis Acid-Bronsted Base Cooperative Catalysis -- 1.3.1 Cooperative Catalysts Based on a 1,1'-Binaphthol Ligand Platform -- 1.3.1.1 Heterobimetallic Catalysts -- 1.3.1.2 Cooperative Catalysts Based on Linked-BINOL -- 1.3.2 Cooperative Catalysts Based on a Salen and Schiff Base Ligand Platform -- 1.3.3 Cooperative Catalysts Based on a Ligand Platform Derived from Amino Acids -- 1.4 Soft Lewis Acid-Bronsted Base Cooperative Catalysis -- 1.5 Conclusion -- References -- Chapter 2 Lewis Acid-Lewis Base Catalysis -- 2.1 Introduction -- 2.2 Lewis Acid and Lewis Base Activation -- 2.2.1 Modes of Activation -- 2.2.2 Self-Quenching -- 2.3 Addition to Carbonyl Compounds -- 2.3.1 Reduction of Ketones -- 2.3.2 Alkylation of Aldehydes and Ketones -- 2.3.3 Allylation of Aldehydes and Ketones -- 2.3.3.1 Lewis Acid/Lewis Base Activation -- 2.3.3.2 Lewis Base Nucleophilic/Electrophilic Activation of Allylsilanes -- 2.3.4 Cyanation of Aldehydes, Ketones, and Imines -- 2.3.4.1 Silylcyanation -- 2.3.4.2 Cyanoformylation and Cyanophosphorylation -- 2.3.4.3 Cyanoacylation -- 2.4 Condensation Reactions -- 2.4.1 Aldol Reactions -- 2.4.2 Mannich Reactions -- 2.5 Morita-Baylis-Hillman Reactions -- 2.6 Epoxide Openings -- 2.6.1 Coupling with CO2 and CS2 -- 2.7 Cyclization Reactions -- 2.7.1 [2+2] Cycloadditions -- 2.7.2 [3+2] Cycloadditions -- 2.7.3 [4+2] Additions -- 2.8 Polymerizations -- 2.9 Conclusions and Outlook -- References -- Chapter 3 Cooperating Ligands in Catalysis -- 3.1 Introduction.

3.2 Chemically Active Ligands Assisting a Metal-Localized Catalytic Reaction -- 3.2.1 Cooperating Ligands with a Pendant Basic Site -- 3.2.1.1 Functional Sites Located in the First Coordination Sphere of a Metal Complex -- 3.2.1.2 Basic Functional Sites Located in the Outer Coordination Sphere -- 3.2.2 Remote Pendant Basic Sites and Reorganization of π Systems as Driving Forces for Metal-Ligand Cooperativity -- 3.2.3 Metal-Ligand Cooperation with a Pendant Acid Site -- 3.3 Redox-Active Ligands Assisting Metal-Based Catalysts -- 3.3.1 Redox-Active Ligands as Electron Reservoirs -- 3.3.2 Redox-Active Ligands Participating in Direct Substrate Activation -- 3.4 Summary -- References -- Chapter 4 Cooperative Enamine-Lewis Acid Catalysis -- 4.1 Introduction -- 4.1.1 Challenge in Combining Enamine Catalysis with Lewis Acid Catalysis -- 4.2 Reactions Developed through Cooperative Enamine-Lewis Acid Catalysis -- 4.2.1 α-Alkylation of Carbonyl Compounds -- 4.2.1.1 α-Allylation of Aldehydes and Ketones -- 4.2.1.2 α-Propargylation of Aldehydes -- 4.2.1.3 α-Alkenylation and α-Arylation of Aldehydes -- 4.2.1.4 α-Trifluoromethylation of Aldehydes Through Enamine Addition to Togni's Reagent -- 4.2.2 Asymmetric Direct Aldol Reactions -- 4.2.2.1 Asymmetric Direct Aldol Reactions Catalyzed by Bifunctional Amine-Boronic Acid Catalysts -- 4.2.2.2 Asymmetric Direct Aldol Reactions Catalyzed by Bifunctional Amine-Metal Lewis Acid Catalysts -- 4.2.2.3 Enamine Addition to Ynals Activated by Metal π-Acids -- 4.2.2.4 Asymmetric Direct Aldol Reactions by Cooperative Arylamine-Metal Lewis Acid Catalysis -- 4.2.3 Asymmetric Hetero-Diels-Alder Reactions -- 4.2.3.1 Asymmetric Inverse-Electron Demand Oxa-Diels-Alder Reactions of Ketones and Activated Enones.

4.2.3.2 Asymmetric Three-Component Inverse-Electron-Demand Aza-Diels-Alder Reactions of Ketones and Activated Enones -- 4.2.3.3 Oxa-Diels-Alder Reaction of Isatins and Acyclic α,β-Unsaturated Methyl Ketones through Cooperative Dienamine and Metal Lewis Acid Catalysis -- 4.2.4 Asymmetric Michael Addition Reactions -- 4.3 Conclusion -- Acknowledgment -- References -- Chapter 5 Hydrogen Bonding-Mediated Cooperative Organocatalysis by Modified Cinchona Alkaloids -- 5.1 Introduction -- 5.2 The Emergence of Highly Enantioselective Base Organocatalysis -- 5.3 Hydrogen Bonding-Based Cooperative Catalysis by Modified Cinchona Alkaloids -- 5.3.1 The Emergence of Modified Cinchona Alkaloids as Bifunctional Catalysts -- 5.3.2 The Development of Modified Cinchona Alkaloids as Broadly Effective Bifunctional Catalysts -- 5.3.3 Multifunctional Cooperative Catalysis by Modified Cinchona Alkaloids -- 5.3.3.1 Asymmetric Tandem Conjugate Addition-Protonation Reactions -- 5.3.3.2 Catalytic Asymmetric Isomerization of Olefin and Imines -- 5.3.4 Selective Examples of Synthetic Applications -- 5.4 Conclusion and Outlooks -- Acknowledgments -- References -- Chapter 6 Cooperation of Transition Metals and Chiral Bronsted Acids in Asymmetric Catalysis -- 6.1 General Introduction -- 6.2 Cooperative Catalysis of Palladium(II) and a Bronsted Acid -- 6.3 Cooperative Catalysis of Palladium(0) and a Bronsted Acid -- 6.4 Cooperative Catalysis of a Rhodium Complex and a Bronsted Acid -- 6.5 Cooperative Catalysis of a Silver Complex and a Bronsted Acid -- 6.6 Cooperative Catalysis of a Copper Complex and a Bronsted Acid -- 6.7 Cooperative Catalysis of an Iridium Complex and a Bronsted Acid -- 6.8 Cooperative Catalysis of an Iron Complex and a Bronsted Acid -- 6.9 Perspective -- References.

Chapter 7 Cooperative Catalysis Involving Chiral Ion Pair Catalysts -- 7.1 Introduction -- 7.2 Chiral Cation-Based Catalysis -- 7.2.1 Cooperative Combination of Chiral Cation-Based Catalysts and Transition-Metal Catalysts -- 7.2.2 Bifunctional Chiral Cation-Based Catalysts -- 7.2.2.1 Free-OH-Containing Catalysts -- 7.2.2.2 Onium Salt Catalysts Containing Alternative H-Bonding Donors -- 7.2.2.3 Lewis Acid-Containing Bifunctional Catalysts -- 7.2.2.4 Betaines -- 7.2.3 Chiral Cation-Based Catalysts Containing a Catalytically Relevant Achiral Counteranion -- 7.3 Chiral Anion Based Catalysis -- 7.3.1 Cooperative Organocatalytic Approaches Involving a Chiral Anion in Ion-Pairing Catalysts -- 7.3.2 Chiral Anion Catalysis in Combination with Metal Catalysis -- 7.3.3 Cooperative Use of H-Bonding Catalysts for Anion Binding and Complementary Activation Modes -- 7.4 Synopsis -- References -- Chapter 8 Bimetallic Catalysis: Cooperation of Carbophilic Metal Centers -- 8.1 Introduction -- 8.2 Homobimetallic Catalysts -- 8.2.1 Cooperation of Two Palladium Centers -- 8.2.1.1 Reactions Providing Achiral or Racemic Products -- 8.2.1.2 Enantioselective Reactions -- 8.2.2 Cooperation of Two Gold Centers -- 8.2.3 Cooperation of Two Nickel Centers -- 8.2.4 Cooperation of Two Rh or Ir Centers -- 8.3 Heterobimetallic Catalysts -- 8.3.1 Cooperation of a Pd Center with a Different Metal Center -- 8.3.1.1 Enantioselective Reactions -- 8.3.1.2 Nonenantioselective Reactions -- 8.3.2 Cooperation of a Ni Center with another Metal Center -- 8.3.3 Cooperation of a Cu or Ag Center with another Metal Center (Not~Pd) -- 8.4 Synopsis -- Acknowledgments -- References -- Chapter 9 Cooperative H2 Activation by Borane-Derived Frustrated Lewis Pairs -- 9.1 Introduction -- 9.2 Mechanistic Considerations -- 9.3 General Considerations.

9.3.1 Choice of Lewis Base -- 9.3.2 Choice of Lewis Acid -- 9.3.3 Intramolecular Frustrated Lewis Pairs -- 9.4 Hydrogenation of Imines -- 9.5 Hydrogenation of Enamines and Silylenol Ethers -- 9.6 Hydrogenation of Heterocycles -- 9.7 Hydrogenation of Enones, Alkylidene Malonates, and Nitroolefins -- 9.8 Hydrogenation of Unpolarized Olefins and Polycyclic Aromatic Hydrocarbons -- 9.9 Summary -- Abbreviations -- References -- Chapter 10 Catalysis by Artificial Oligopeptides -- 10.1 Cooperative Catalysis by Short Peptides -- 10.1.1 Unstructured Sequences -- 10.1.2 Structured Sequences -- 10.2 Cooperative Catalysis by Supramolecular Systems -- 10.2.1 Unimolecular Receptors/Catalysts -- 10.2.2 Molecular Aggregates -- 10.3 Cooperative Catalysis by Nanosystems -- 10.3.1 Dendrimer-Based Catalysts -- 10.3.2 Nanoparticle-Based Catalysts -- 10.4 Conclusions -- References -- Chapter 11 Metals and Metal Complexes in Cooperative Catalysis with Enzymes within Organic-Synthetic One-Pot Processes -- 11.1 Introduction -- 11.2 Metal-Catalyzed In situ-Preparation of an Enzyme's Reagent (Cofactor) Required for the Biotransformation -- 11.2.1 Overview About the Concept of In situ-Cofactor Recycling in Enzymatic Redox Processes -- 11.2.2 Metal-Catalyzed In situ-Recycling of Reduced Cofactors NAD(P)H for Enzymatic Reduction Reactions -- 11.2.3 Metal-Catalyzed In situ-Recycling of Oxidized Cofactors NAD(P)+ for Enzymatic Oxidation Reactions -- 11.3 Combination of a Metal-Catalyzed Racemization of a Substrate with a Stereoselective Biotransformation Toward a Dynamic Kinetic Resolution.

11.3.1 Dynamic Kinetic Resolution Based on Metal-Catalyzed Racemization of the Substrate in Combination with Enzymatic Resolution in Aqueous Media.