Cooperative Catalysis: Designing Efficient Catalysts for Synthesis

Cooperative Catalysis: Designing Efficient Catalysts for Synthesis

By: Rene Peters (author)Hardback

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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 / Bronsted 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.

About Author

Rene 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 Zurich 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.

Contents

Preface XIII Acknowledgments XVII List of Contributors XIX 1 Lewis Acid Bronsted Base Catalysis 1 Masakatsu Shibasaki and Naoya Kumagai 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 1.3.2 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 Bronsted 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 Monica Trincado and Hansjorg Grutzmacher 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 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 -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 Bronsted 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 Bronsted Acid 172 6.3 Cooperative Catalysis of Palladium(0) 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 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 Rene 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 Groger 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

Product Details

  • ISBN13: 9783527336890
  • Format: Hardback
  • Number Of Pages: 456
  • ID: 9783527336890
  • weight: 1120
  • ISBN10: 3527336893

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