Cooperative catalysis : designing efficient catalysts for synthesis / edited by René Peters.

Format:

Book

Contributor:

Peters, René, 1971- editor.

Language:

English

Subjects (All):

Catalysts.

Catalysis.

Organic compounds--Synthesis.

Organic compounds.

Physical Description:

xxi, 427 pages : illustrations ; 25 cm

Edition:

First edition.

Place of Publication:

Weinheim, Germany : Wiley-VCH Verlag GmbH & Co. KGaA, 2015.

Summary:

Written by experts in the field, this is a much-needed overview of the rapidly emerging field of cooperative catalysis. The authors focus on the design and development of novel high-performance catalysts for applications in organic synthesis (particularly asymmetric synthesis), covering a broad range of topics, from the latest progress in Lewis acid / Bransted base catalysis to e.g. metal-assisted organo catalysis, cooperative metal/enzyme catalysis, and cooperative catalysis in polymerization reactions and on solid surfaces. The chapters are classified according to the type of cooperating activating groups, and describe in detail the different strategies of cooperative activation, highlighting their respective advantages and pitfalls. As a result, readers will learn about the different concepts of cooperative catalysis, their corresponding modes of operation and their applications, thus helping to find a solution to a specific synthetic catalysis problem. Book jacket.

Contents:

1 Lewis Acid-Bronsted Base Catalysis / Masakatsu Shibasaki Shibasaki, Masakatsu, Naoya Kumagai Kumagai, Naoya 1

1.1 Introduction 1

1.2 Lewis Acid-Bronsted Base Catalysis in Metalloenzymes 1

1.3 Hard Lewis Acid-Bronsted Base Cooperative Catalysis 3

1.3.1 Cooperative Catalysts Based on a 1,1'-Binaphthol Ligand Platform 3

1.3.1.1 Heterobimetallic Catalysts 3

1.3.1.2 Cooperative Catalysts Based on Linked-BLNOL 8

1.3.2 Cooperative Catalysts Based on a Salen and Schiff Base Ligand Platform 11

1.3.3 Cooperative Catalysts Based on a Ligand Platform Derived from Amino Acids 17

1.4 Soft Lewis Acid-Brønsted Base Cooperative Catalysis 21

1.5 Conclusion 24

References 25

2 Lewis Acid-Lewis Base Catalysis / Christina Moberg Moberg, Christina 35

2.1 Introduction 35

2.2 Lewis Acid and Lewis Base Activation 35

2.2.1 Modes of Activation 35

2.2.2 Self-Quenching 37

2.3 Addition to Carbonyl Compounds 38

2.3.1 Reduction of Ketones 38

2.3.2 Alkylation of Aldehydes and Ketones 39

2.3.3 Allylation of Aldehydes and Ketones 41

2.3.3.1 Lewis Acid/Lewis Base Activation 41

2.3.3.2 Lewis Base Nucleophilic/Electrophilic Activation of Allylsilanes 42

2.3.4 Cyanation of Aldehydes, Ketones, and Imines 43

2.3.4.1 Silylcyanation 43

2.3.4.2 Cyanoformylation and Cyanophosphorylation 45

2.3.4.3 Cyanoacylation 46

2.4 Condensation Reactions 47

2.4.1 Aldol Reactions 47

2.4.2 Mannich Reactions 48

2.5 Morita-Baylis-Hillman Reactions 48

2.6 Epoxide Openings 50

2.6.1 Coupling with CO₂ and CS₂ 50

2.7 Cyclization Reactions 51

2.7.1 [2+2] Cycloadditions 51

2.7.2 [3+2] Cycloadditions 56

2.7.3 [4+2] Additions 58

2.8 Polymerizations 60

2.9 Conclusions and Outlook 61

References 62

3 Cooperating Ligands in Catalysis / Monica Trincado Trincado, Monica, Hansjörg Grutzmacher Grutzmacher, Hansjörg 67

3.1 Introduction 67

3.2 Chemically Active Ligands Assisting a Metal-Localized Catalytic Reaction 67

3.2.1 Cooperating Ligands with a Pendant Basic Site 67

3.2.1.1 Functional Sites Located in the First Coordination Sphere of a Metal Complex 68

3.2.1.2 Basic Functional Sites Located in the Outer Coordination Sphere 83

3.2.2 Remote Pendant Basic Sites and Reorganization of ft Systems as Driving Forces for Metai-Ligand Cooperativity 89

3.2.3 Metal-Ligand Cooperation with a Pendant Acid Site 94

3.3 Redox-Active Ligands Assisting Metal-Based Catalysts 96

3.3.1 Redox-Active Ligands as Electron Reservoirs 96

3.3.2 Redox-Active Ligands Participating in Direct Substrate Activation 101

3.4 Summary 104

References 105

4 Cooperative Enamine-Lewis Acid Catalysis / Hong Wang Wang, Hong, Yongming Deng Deng, Yongming 111

4.1 Introduction 111

4.1.1 Challenge in Combining Enamine Catalysis with Lewis Acid Catalysis 112

4.2 Reactions Developed through Cooperative Enamine-Lewis Acid Catalysis 113

4.2.1 α-Alkylation of Carbonyl Compounds 114

4.2.1.1 α-Allylation of Aldehydes and Ketones 115

4.2.1.2 α-Propargylation of Aldehydes 125

4.2.1.3 α-Alkenylation and a-Arylation of Aldehydes 127

4.2.1.4 α-Trifluoromethylation of Aldehydes Through Enamine Addition to Togni's Reagent 131

4.2.2 Asymmetric Direct Aldol Reactions 133

4.2.2.1 Asymmetric Direct Aldol Reactions Catalyzed by Bifunctional Amine-Boronic Acid Catalysts 133

4.2.2.2 Asymmetric Direct Aldol Reactions Catalyzed by Bifunctional Amine-Metal Lewis Acid Catalysts 1.33

4.2.2.3 Enamine Addition to Ynals Activated by Metal π-Acids 134

4.2.2.4 Asymmetric Direct Aldol Reactions by Cooperative Arylamine-Metal Lewis Acid Catalysis 135

4.2.3 Asymmetric Hetero-Diels-AIder Reactions 136

4.2.3.1 Asymmetric Inverse-Electron Demand Oxa-Diels-Alder Reactions of Ketones and Activated Enones 136

4.2.3.2 Asymmetric Three-Component Inverse-Electron-Demand Aza-Diels-Alder Reactions of Ketones and Activated Enones 136

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 138

4.2.4 Asymmetric Michael Addition Reactions 138

4.3 Conclusion 139

Acknowledgment 140

References 140

5 Hydrogen Bonding-Mediated Cooperative Organocatalysis by Modified Cinchona Alkaloids / Xiaojie Lu Lu, Xiaojie, Li Deng Deng, Li 145

5.1 Introduction 145

5.2 The Emergence of Highly Enantioselective Base Organocatalysis 145

5.3 Hydrogen Bonding-Based Cooperative Catalysis by Modified Cinchona Alkaloids 151

5.3.1 The Emergence of Modified Cinchona Alkaloids as Bifunctional Catalysts 151

5.3.2 The Development of Modified Cinchona Alkaloids as Broadly Effective Bifunctional Catalysts 153

5.3.3 Multifunctional Cooperative Catalysis by Modified Cinchona Alkaloids 159

5.3.3.1 Asymmetric Tandem Conjugate Addition-Protonation Reactions 159

5.3.3.2 Catalytic Asymmetric Isomerization of Olefin and Imines 161

5.3.4 Selective Examples of Synthetic Applications 164

5.4 Conclusion and Outlooks 167

Acknowledgments 167

References 167

6 Cooperation of Transition Metals and Chiral Bronsted Acids in Asymmetric Catalysis / Hua Wu Wu, Hua, Yu-Ping He He, Yu-Ping, Liu-Zhu Gong Gong, Liu-Zhu 171

6.1 General Introduction 171

6.2 Cooperative Catalysis of Palladium(II) and a Bransted Acid 172

6.3 Cooperative Catalysis of Palladium(O) and a Bronsted Acid 175

6.4 Cooperative Catalysis of a Rhodium Complex and a Bronsted Acid 179

6.5 Cooperative Catalysis of a Silver Complex and a Bronsted Acid 187

6.6 Cooperative Catalysis of a Copper Complex and a Bronsted Acid 188

6.7 Cooperative Catalysis of an Iridium Complex and a Bronsted Acid 189

6.8 Cooperative Catalysis of an Iron Complex and a Bronsted Acid 191

6.9 Perspective 193 References 193

7 Cooperative Catalysis Involving Chiral Ion Pair Catalysts / Mario Waser Waser, Mario, Johanna Novacek Novacek, Johanna, Katharina Gratzer Gratzer, Katharina 197

7.1 Introduction 197

7.2 Chiral Cation-Based Catalysis 198

7.2.1 Cooperative Combination of Chiral Cation-Based Catalysts and Transition-Metal Catalysts 199

7.2.2 Bifunctional Chiral Cation-Based Catalysts 200

7.2.2.1 Free-OH-Containing Catalysts 201

7.2.2.2 Onium Salt Catalysts Containing Alternative H-Bonding Donors 207

7.2.2.3 Lewis Acid-Containing Bifunctional Catalysts 210

7.2.2.4 Betaines 211

7.2.3 Chiral Cation-Based Catalysts Containing a Catalytically Relevant Achiral Counteranion 212

7.3 Chiral Anion Based Catalysis 216

7.3.1 Cooperative Organocatalytic Approaches Involving a Chiral Anion in Ion-Pairing Catalysts 216

7.3.2 Chiral Anion Catalysis in Combination with Metal Catalysis 217

7.3.3 Cooperative Use of H-Bonding Catalysts for Anion Binding and Complementary Activation Modes 220

7.4 Synopsis 221

References 222

8 Bimetallic Catalysis: Cooperation of Carbophilic Metal Centers / Marcel Weiss Weiss, Marcel, Rene Peters Peters, Rene 227

8.1 Introduction 227

8.2 Homobimetallic Catalysts 228

8.2.1 Cooperation of Two Palladium Centers 228

8.2.1.1 Reactions Providing Achiral or Racemic Products 229

8.2.1.2 Enantioselective Reactions 233

8.2.2 Cooperation of Two Gold Centers 238

8.2.3 Cooperation of Two Nickel Centers 242

8.2.4 Cooperation of Two Rh or Ir Centers 243

8.3 Heterobimetallic Catalysts 246

8.3.1 Cooperation of a Pd Center with a Different Metal Center 246

8.3.1.1 Enantioselective Reactions 246

8.3.1.2 Nonenantioselective Reactions 249

8.3.2 Cooperation of a Ni Center with another Metal Center 255

8.3.3 Cooperation of a Cu or Ag Center with another Metal Center (Not Pd) 257

8.4 Synopsis 258

Acknowledgments 259

References 259

9 Cooperative H₂ Activation by Borane-Derived Frustrated Lewis Pairs / Jan Parodies Parodies, Jan 263

9.1 Introduction 263

9.2 Mechanistic Considerations 264

9.3 General Considerations 267

9.3.1 Choice of Lewis Base 267

9.3.2 Choice of Lewis Acid 268

9.3.3 Intramolecular Frustrated Lewis Pairs 270

9.4 Hydrogenation of Imines 273

9.5 Hydrogenation of Enamines and Silylenol Ethers 276

9.6 Hydrogenation of Heterocycles 279

9.7 Hydrogenation of Enones, Alkylidene Malonates, and Nitrooleftns 282

9.8 Hydrogenation of Unpolarized Olefins and Polycyclic Aromatic Hydrocarbons 286

9.9 Summary 290 Abbreviations 290 References 291

10 Catalysis by Artificial Oligopeptides / Fabrizio Mancin Mancin, Fabrizio, Leonard J. Prins Prins, Leonard J., Paolo Scrimin Scrimin, Paolo 295

10.1 Cooperative Catalysis by Short Peptides 295

10.1.1 Unstructured Sequences 295

10.1.2 Structured Sequences 299

10.2 Cooperative Catalysis by Supramolecular Systems 307

10.2.1 Unimolecular Receptors/Catalysts 307

10.2.2 Molecular Aggregates 309

10.3 Cooperative Catalysis by Nanosystems 312

10.3.1 Dendrimer-Based Catalysts 312

10.3.2 Nanoparticle-Based Catalysts 315

10.4 Conclusions 320

References 321

11 Metals and Metal Complexes in Cooperative Catalysis with Enzymes within Organic-Synthetic One-Pot Processes / Haratd Gröger Gröger, Haratd 325

11.1 Introduction 325

11.2 Metal-Catalyzed In situ-Preparation of an Enzyme's Reagent (Cofactor) Required for the Biotransformation 328

11.2.1 Overview About the Concept of In situ-Cofactor Recycling in Enzymatic Redox Processes 328

11.2.2 Metal-Catalyzed In situ-Recycling of Reduced Cofactors NAD(P)H for Enzymatic Reduction Reactions 330

11.2.3 Metal-Catalyzed In situ-Recycling of Oxidized Cofactors NAD(P)+ for Enzymatic Oxidation Reactions 331

11.3 Combination of a Metal-Catalyzed Racemization of a Substrate with a Stereoselective Biotransformation Toward a Dynamic Kinetic Resolution 332

11.3.1 Dynamic Kinetic Resolution Based on Metal-Catalyzed Racemization of the Substrate in Combination with Enzymatic Resolution in Aqueous Media 332

11.3.2 Dynamic Kinetic Resolution Based on Metal-Catalyzed Racemization of the Substrate in Combination with Enzymatic Resolution in Organic Media 334

11.4 Combinations of Metal Catalysis and Biocatalysis Toward "Consecutive" One-Pot Processes without Intermediate Isolation 339

11.4.1 Introduction of the Concepts of "Consecutive" One-Pot Processes without Intermediate Isolation 339

11.4.2 "Consecutive" One-Pot Processes Running in a Tandem-Mode 339

11.4.3 "Consecutive" One-Pot Processes with Completion of the Initial Reaction Prior to Catalyst Addition for the Second Step 343

11.5 Summary and Outlook 347

References 347

12 Cooperative Catalysis on Solid Surfaces versus Soluble Molecules / Michael M. Nigra Nigra, Michael M., Alexander Katz Katz, Alexander 351

12.1 Introduction 351

12.2 Tuning Cooperativity of Acid- Base Bifunctional Groups by Varying the Distance Between Them in a Soluble-Molecule Platform 352

12.3 Acid-Base Bifunctional Catalysts on Two-Dimensional Surfaces: Organic-Inorganic Materials 356

12.4 Cooperative Catalysis on Surfaces versus Soluble Molecular Platforms for Kinetic Resolution of Racemic Epoxides 362

12.5 Depolymerization of Biomass Polymers via Cooperative Catalysis on Surfaces 365

12.6 Conclusions 370

References 370

13 Cooperative Catalysis in Polymerization Reactions / Malte Winnacker Winnacker, Malte, Sergei Vagin Vagin, Sergei, Bemhard Rieger Rieger, Bemhard 373

13.1 Introduction 373

13.2 Cooperative Effects for the Polymerization of Lactide and Other Cyclic Esters 374

13.3 Polymerization Reactions of Vinyl Monomers with Frustrated Lewis Pairs 385

13.4 Zinc-Based Cooperative Catalysis of Epoxide/CO₂ Copolymerization 390

13.5 Cooperative Mechanism of Epoxide/C02 Copolymerization by Salen-Type Complexes 402

13.6 Summary 413

References 414.

Notes:

Includes bibliographical references and index.

ISBN:

9783527336890

3527336893

OCLC:

907794951