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Cooperative Catalysis: Designing Efficient Catalysts for Synthesis

ISBN: 978-3-527-33689-0
456 pages
April 2015
Cooperative Catalysis: Designing Efficient Catalysts for Synthesis (3527336893) cover image

Description

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 / Br°nsted 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.
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Table of Contents

Preface XIII

Acknowledgments XVII

List of Contributors XIX

1 Lewis Acid–Brønsted Base Catalysis 1
Masakatsu Shibasaki and Naoya Kumagai

1.1 Introduction 1

1.2 Lewis Acid–Brønsted Base Catalysis in Metalloenzymes 1

1.3 Hard Lewis Acid–Brønsted Base Cooperative Catalysis 3

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

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 35
Christina Moberg

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

2.3.4 Cyanation of Aldehydes, Ketones, and Imines 43

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 67
Mónica Trincado and Hansjörg Grützmacher

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

3.2.2 Remote Pendant Basic Sites and Reorganization of π Systems as Driving Forces for Metal–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 111
HongWang and Yongming Deng

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

4.2.2 Asymmetric Direct Aldol Reactions 133

4.2.3 Asymmetric Hetero-Diels-Alder Reactions 136

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 145
Xiaojie Lu and Li Deng

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

5.3.4 Selective Examples of Synthetic Applications 164

5.4 Conclusion and Outlooks 167

Acknowledgments 167

References 167

6 Cooperation of Transition Metals and Chiral Brønsted Acids in Asymmetric Catalysis 171
HuaWu, Yu-PingHe, and Liu-ZhuGong

6.1 General Introduction 171

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

6.3 Cooperative Catalysis of Palladium(0) and a Brønsted Acid 175

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

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

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

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

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

6.9 Perspective 193

References 193

7 Cooperative Catalysis Involving Chiral Ion Pair Catalysts 197
MarioWaser, Johanna Novacek, and Katharina Gratzer

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

7.2.3 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 CarbophilicMetal Centers 227
MarcelWeiss and René Peters

8.1 Introduction 227

8.2 Homobimetallic Catalysts 228

8.2.1 Cooperation of Two Palladium Centers 228

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

8.3.2 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 263
Jan Paradies

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 Nitroolefins 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 295
Fabrizio Mancin, Leonard J. Prins, and Paolo Scrimin

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 325
Harald Gröger

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 SolubleMolecules 351
Michael M. Nigra and Alexander Katz

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 373
MalteWinnacker, Sergei Vagin, and Bernhard Rieger

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/CO2 Copolymerization by Salen-Type Complexes 402

13.6 Summary 413

References 414

Index 417

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Author Information

RenÚ Peters is professor for Organic Chemistry at the University of Stuttgart, Germany. He studied chemistry at the RWTH Aachen (Germany) and received his doctoral degree in 2000 under supervision of Prof. Dieter Enders. For his postdoctoral studies he joined the group of Prof. Yoshito Kishi at Harvard University, USA. Afterwards, he worked for three years as a process research chemist at F. Hoffmann-La Roche in Basel, Switzerland. In 2004, he joined the faculty of ETH ZŘrich as assistant professor and since 2008 he holds his current position. His research efforts are mainly directed towards the development of efficient catalytic asymmetric methodologies, in particular using cooperative catalysis.
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