Recoverable and Recyclable Catalysts

Recoverable and Recyclable Catalysts There is continued pressure on chemical and pharmaceutical industries to reduce chemical waste and improve the selectivity and efficiency of synthetic processes. The need to implement green chemistry principles is a driving force towards the development of recoverable and recyclable catalysts. The design and synthesis of recoverable catalysts is a highly challenging interdisciplinary field combining chemistry, materials science engineering with economic and environmental objectives. Drawing on international research and highlighting recent developments, this book serves as a practical guide for both experts and newcomers to the field. Topics covered include: An introduction to the principles of catalyst recovery and recycling Catalysts on insoluble and soluble support materials Thermomorphic catalysts, self-supported catalysts and perfluorous catalytic systems The development of reusable organic catalysts Continuous flow and membrane reactors Each chapter combines principles with practical information on the synthesis of catalysts and strategies for catalyst recovery. The book concludes with a comparison of different catalytic systems, using case studies to illustrate the key features of each approach. Recoverable and Recyclable Catalysts is a valuable reference source for academic researchers and professionals from a range of pharmaceutical and chemical industries, particularly those working in catalysis, organic synthesis and sustainable chemistry.

Preface xiii Acknowledgements xv Contributors xvii 1 The Experimental Assay of Catalyst Recovery: General Concepts 1 John A. Gladysz 1.1 Introduction 1 1.2 Catalyst Precursor vs Catalyst 2 1.3 Catalyst vs Catalyst Resting State 3 1.4 Catalyst Inventory: Loss Mechanisms 5 1.5 Evaluation of Catalyst Recovery 8 1.6 Prospective 13 2 Surface-functionalized Nanoporous Catalysts for Renewable Chemistry 15 Brian G. Trewyn, Hung-Ting Chen and Victor S.-Y. Lin 2.1 Introduction 15 2.2 Immobilization Strategies of Heterogeneous Catalysts 17 2.3 Efficient Heterogeneous Catalysts with Enhanced Reactivity and Selectivity with Functionality 26 2.4 Other Heterogeneous Catalyst Systems on Nonsilica Supports 44 2.5 Conclusion 45 3 Insoluble Resin-supported Catalysts 49 Gang Zhao and Zhuo Chai 3.1 Introduction 49 3.2 Transition Metal catalyzed c c Bond Formation Reactions 50 3.3 Oxidation 56 3.4 Reduction 61 3.5 Organocatalyzed Reactions 62 3.6 Annulation Reactions 66 3.7 Miscellaneous 70 3.8 Conclusion 72 4 Catalysts Bound to Soluble Polymers 77 Tamilselvi Chinnusamy, Petra Hilgers and Oliver Reiser 4.1 Introduction 77 4.2 Soluble Supports – General Considerations 78 4.3 Recent Developments of Soluble Polymer-supported Catalysts 79 4.4 Recent Examples for Reactions Promoted by Catalysts Bound to Soluble Polymers 81 4.5 Conclusion 98 5 Polymeric, Recoverable Catalytic Systems 101 Qiao-Sheng Hu 5.1 Introduction 101 5.2 Polymeric Catalyst Systems 102 5.3 Summary 114 6 Thermomorphic Catalysts 117 David E. Bergbreiter 6.1 Introduction 117 6.2 Thermomorphic Catalyst Separation Strategies 118 6.3 Hydrogenation Reactions Under Thermomorphic Conditions 122 6.4 Hydroformylation Reactions Under Thermomorphic Conditions 126 6.5 Hydroaminations Under Thermomorphic Conditions 129 6.6 Pd-catalyzed Reactions Under Thermomorphic Conditions 130 6.7 Polymerization Reactions Under Thermomorphic Conditions 138 6.8 Organocatalysis Under Thermomorphic Conditions 142 6.9 Cu(I)-catalyzed 1,3-Dipolar Cycloadditions Under Thermomorphic Conditions 144 6.10 Thermomorphic Hydrosilylation Catalysts 144 6.11 Thermomorphic Catalytic Oxidations 145 6.12 Conclusions 147 7 Self-supported Asymmetric Catalysts 155 Wenbin Lin and David J. Mihalcik 7.1 Introduction 155 7.2 Self-supported Asymmetric Catalysts Formed by Linking Catalytically Active Subunits via Metal–Ligand Coordination 156 7.3 Self-supported Asymmetric Catalysts Formed by Post-synthetic Modifications of Coordination Polymers 163 7.4 Self-supported Asymmetric Catalysts Formed by Linking Multitopic Chiral Ligands with Catalytic Metal Centers 168 7.5 Conclusions and Outlook 172 8 Fluorous Chiral Catalyst Immobilization 179 Tibor Soos 8.1 Introduction 179 8.2 Fluorous Chemistry and its Basic Recovery Concepts 180 8.3 Application of Fluorous Chiral Catalysts 181 8.4 Summary 196 9 Biphasic Catalysis: Catalysis in Supercritical CO2 and in Water 199 Simon L. Desset and David J. Cole-Hamilton 9.1 Introduction 199 9.2 Biphasic Catalysis 200 9.3 Aqueous Biphasic Catalysis 202 9.4 Supercritical Carbon Dioxide 229 9.5 Conclusion 246 10 Asymmetric Catalysis in Ionic Liquids 259 Lijin Xu and Jianliang Xiao 10.1 Introduction 259 10.2 Metal-catalyzed Asymmetric Reactions in ILs 261 10.3 Asymmetric Organocatalytic Reactions in ILs 287 10.4 Concluding Remarks 294 11 Recoverable Organic Catalysts 301 Maurizio Benaglia 11.1 Introduction 301 11.2 Achiral Organic Catalysts 304 11.3 Chiral Organic Catalysts 311 11.4 Catalysts Derived from Amino Acids 319 11.5 General Considerations on Recyclable Organocatalysts 334 11.6 Outlook and Perspectives 336 12 Organic Polymer-microencapsulated Metal Catalysts 341 Jun Ou and Patrick H. Toy 12.1 Introduction 341 12.2 Non-cross-linked Polymer-microencapsulated Catalysts 342 12.3 Cross-linked Polymer-microencapsulated Catalysts 355 12.4 Summary Table 374 12.5 Conclusions 375 13 Organic Synthesis with Mini Flow Reactors Using Immobilised Catalysts 379 Sascha Ceylan and Andreas Kirschning 13.1 Introduction 379 13.2 Catalysis in Mini Flow Reactors with Immobilised Catalysts 382 13.3 Miscellaneous Enabling Techniques for Mini Flow Systems 404 13.4 Perspectives and Outlook 406 14 Homogeneous Catalysis Using Microreactor Technology 411 Johan C. Brandt and Thomas Wirth 14.1 Introduction 411 14.2 Acid-catalysed Reactions 411 14.3 Liquid–liquid Biphasic Systems 413 14.4 Photocatalysis 418 14.5 Asymmetric Catalytic Reactions 421 14.6 Unusual Reaction Conditions 421 15 Catalyst Immobilization Strategy: Some General Considerations and a Comparison of the Main Features of Different Supports 427 Franco Cozzi 15.1 Introduction 427 15.2 General Considerations on Catalyst Immobilization 428 15.3 Comparison of Different Supports Employed for the Immobilization of Proline 442 15.4 Comparison of Different Supports Employed for the Immobilization of Bis(oxazolines) 452 15.5 Conclusions 458 References 458 Index 463