Preface XV List of Contributors XIX 1 Acid?Base Cooperative Catalysis for Organic Reactions by Designed Solid Surfaces with Organofunctional Groups 1 Ken Motokura, Toshihide Baba, and Yasuhiro Iwasawa 1.1 Introduction 1 1.2 Bifunctional Catalysts Possessing Both Acidic and Basic Organic Groups 2 1.2.1 Urea?Amine Bifunctional Catalyst 2 1.2.2 Sulfonic or Carboxylic Acid?Amine Bifunctional Catalyst 3 1.3 Bifunctional Catalysts Possessing Basic Organic Groups and Acid Sites Derived from Their Support Surface 7 1.

3.1 Organic Base-Catalyzed Reactions Enhanced by SiO2 7 1.3.2 Amine-Catalyzed Reactions Enhanced by Acid Site on Silica?Alumina 11 1.3.3 Control of Acid?Base Interaction on Solid Surface 13 1.3.4 Cooperative Catalysis of Acid Site, Primary Amine, and Tertiary Amine 18 1.

4 Prospect 19 References 20 2 Catalytic Reactions in or by Room-Temperature Ionic Liquids: Bridging the Gap between Homogeneous and Heterogeneous Catalysis 21 Youquan Deng, Feng Shi, and Qinghua Zhang 2.1 Introduction and Background 21 2.2 Catalysis with IL-Supported or Mediated Metal Nanoparticles 22 2.2.1 Preparation of MNPs in ILs 23 2.2.2 Characterization of IL-Supported or Mediated MNPs 28 2.2.

3 Hydrogenation Reactions 31 2.2.4 IL-Supported Pd NPs 32 2.2.5 IL-Supported Pt and Ir NPs 36 2.2.6 IL-Supported Ru NPs 37 2.2.

6.1 IL-Supported Rh NPs 40 2.2.7 C?C Coupling Reactions 42 2.2.8 Brief Summary 49 2.3 Reactions Catalyzed by Solid-Supported IL: Heterogeneous Catalysis with Homogeneous Performance 50 2.3.

1 Introduction 50 2.3.2 Design, Preparation, and Properties of Silica Gel-Confined IL Catalysts 55 2.3.3 Catalytic Reaction with Supported IL Catalysts 57 2.3.4 Brief Summary 79 2.4 Outlook 80 References 80 3 Heterogeneous Catalysis with Organic?Inorganic Hybrid Materials 85 Sang-Eon Park and Eun-Young Jeong 3.

1 Introduction 85 3.1.1 Ordered Mesoporous Silica 85 3.1.2 Organic?Inorganic Hybrid Materials 88 3.1.3 Heterogeneous Catalysis 89 3.2 Organic?Inorganic Hybrid Materials 91 3.

2.1 General Advantages of Organic?Inorganic Hybrid Materials 91 3.2.2 Grafting and Co-Condensation 91 3.2.3 Periodic Mesoporous Organosilicas (PMOs) 96 3.3 Catalysis of Organic?Inorganic Hybrid Materials 99 3.3.

1 Catalytic Application of Organic-Functionalized Mesoporous Silica by Grafting and Co-Condensation Method 99 3.3.2 Catalytic Application of Periodic Mesoporous Organosilica 104 3.3.3 Chiral Catalysis 105 3.3.4 Photocatalysis 106 3.4 Summary and Conclusion 107 References 108 4 Homogeneous Asymmetric Catalysis Using Immobilized Chiral Catalysts 111 Lei Wu, Ji Liu, Baode Ma, and Qing-Hua Fan 4.

1 Introduction 111 4.2 Soluble Polymeric Supports and Catalyst Separation Methods 112 4.2.1 Types of Soluble Polymeric Supports 112 4.2.2 Immobilized Catalyst Separation Methods 114 4.3 Chiral Linear Polymeric Catalysts 114 4.4 Chiral Dendritic Catalysts 126 4.

5 Helical Polymeric Catalysts 139 4.6 Conclusion and Prospects 143 Acknowledgments 146 References 146 5 Endeavors to Bridge the Gap between Homo- and Heterogeneous Asymmetric Catalysis with Organometallics 149 Xingwang Wang, Zheng Wang, and Kuiling Ding 5.1 General Introduction 149 5.2 Combinatorial Approach for Homogeneous Asymmetric Catalysis 151 5.2.1 The Principle of Combinatorial Approach to Chiral Catalyst Discovery 152 5.2.2 Ti(IV)-Catalyzed Enantioselective Reactions 153 5.

2.3 Zn Complex-Catalyzed Enantioselective Reactions 159 5.2.4 Ru Complex-Catalyzed Enantioselective Reactions 168 5.3 Self-Supporting Approach for Heterogeneous Asymmetric Catalysis 172 5.3.1 The Principle of Design and Generation of Self-Supported Catalysts 175 5.3.

2 Self-Supported BINOLate/Ti(IV)-Catalyzed Asymmetric Carbonyl?Ene Reaction 178 5.3.3 Self-Supported BINOLate/Ti(IV)-Catalyzed Asymmetric Sulfoxidation Reaction 178 5.3.4 Self-Supported BINOLate/La(III)-Catalyzed Asymmetric Epoxidation 180 5.3.5 Self-Supported BINOLate/Zn(II)-Catalyzed Asymmetric Epoxidation 183 5.3.

6 Self-Supported Noyori-Type Ru(II)-Catalyzed Asymmetric Hydrogenation 185 5.3.7 Self-Supported MonoPhos/Rh(I)-Catalyzed Asymmetric Hydrogenation Reactions 187 5.4 Conclusions and Outlook 194 Acknowledgments 195 References 195 6 Catalysis in and on Water 201 Shifang Liu and Jianliang Xiao 6.1 Introduction 201 6.2 Catalytic Reactions in and ??on?? Water 202 6.2.1 Hydroformylation 202 6.

2.2 Hydrogenation 208 6.2.3 C?C Bond Formation 220 6.3 Conclusions 244 References 244 7 A Green Chemistry Strategy: Fluorous Catalysis 253 Zhong-Xing Jiang, Xuefei Li, and Feng-Ling Qing 7.1 History of Fluorous Chemistry 253 7.2 Basics of Fluorous Chemistry 254 7.3 Fluorous Metallic Catalysis 263 7.

3.1 Fluorous Palladacycle Catalysts 264 7.3.2 Fluorous Pincer Ligand-Based Catalysts 265 7.3.3 Fluorous Immobilized Nanoparticles Catalysts 267 7.3.4 Fluorous Palladium-NHC Complexes 270 7.

3.5 Fluorous Phosphine-Based Palladium Catalyst 271 7.3.6 Fluorous Grubbs? Catalysts 272 7.3.7 Fluorous Silver Catalyst 273 7.3.8 Fluorous Wilkinson Catalyst 273 7.

3.9 Miscellaneous Fluorous Catalysts 274 7.4 Fluorous Organocatalysis 275 7.4.1 Asymmetric Aldol Reaction 276 7.4.2 Morita?Baylis?Hillman Reaction 277 7.4.

3 Asymmetric Michael Addition Reaction 278 7.4.4 Catalytic Oxidation Reaction 278 7.4.5 Catalytic Acetalization Reaction 279 7.4.6 Catalytic Condensation Reaction 279 7.4.

7 Catalytic Asymmetric Fluorination Reaction 280 7.5 Conclusion 281 References 281 8 Emulsion Catalysis: Interface between Homogeneous and Heterogeneous Catalysis 283 Yan Liu, Zongxuan Jiang, and Can Li 8.1 Introduction 283 8.1.1 Water in Chemistry 283 8.1.2 Water as Solvent 283 8.1.

3 Emulsion 285 8.1.4 Emulsion Catalysis 285 8.2 Emulsion Catalysis in the Oxidative Desulfurization 287 8.2.1 Emulsion Catalytic Oxidative Desulfurization Using H2O2 as Oxidant 287 8.2.2 Emulsion Catalytic Oxidative Desulfurization Using O2 as Oxidant 296 8.

3 Emulsion Catalysis in Lewis Acid-Catalyzed Organic Reactions 297 8.4 Emulsion Catalysis in Reactions with Organocatalysts 303 8.4.1 Aldol Reaction 303 8.4.2 Michael Addition 309 8.5 Emulsion Formed with Polymer-Bounded Catalysts 312 8.5.

1 Emulsion Catalysis Participated by Metal Nanoparticles Stabilized by Polymer 312 8.5.2 Polymer-Bounded Organometallic Catalysts in Emulsion Catalysis 315 8.6 Conclusion and Perspective 319 References 320 9 Identification of Binding and Reactive Sites in Metal Cluster Catalysts: Homogeneous?Heterogeneous Bridges 325 Michael M. Nigra and Alexander Katz 9.1 Introduction 325 9.2 Control of Binding in Metal-Carbonyl Clusters via Ligand Effects 332 9.3 Imaging of CO Binding on Noble Metal Clusters 337 9.

4 Imaging of Open Sites in Metal Cluster Catalysis 339 9.5 Elucidating Kinetic Contributions of Open Sites: Kinetic Poisoning Experiments Using Organic Ligands 340 9.6 More Approaches to Poisoning Open Catalytic Active Sites to Obtain Structure Function Relationships 343 9.6.1 Using Atomic Layer Deposition of Al2O3 to Block Sites on Pd/Al2O3 Catalysts 343 9.6.2 Bromide Poisoning of Active Sites on Au/TiO2 Catalysts for CO Oxidation Reactions 344 9.6.

3 Bromide Poisoning of Active Sites on Au/TiO2 Catalysts for Water-Gas Shift Reactions 345 9.7 Supported Molecular Iridium Clusters for Ethylene Hydrogenation 346 9.8 Summary and Outlook 348 References 349 10 Catalysis in Porous-Material-Based Nanoreactors: a Bridge between Homogeneous and Heterogeneous Catalysis 351 Qihua Yang and Can Li 10.1 Introduction 351 10.2 Preparation of Nanoreactors Based on Porous Materials 352 10.2.1 Mesoporous Silicas 353 10.2.

2 Metal-Organic Frameworks (MOFs) 354 10.2.3 Surface Modification of Nanoreactors 355 10.3 Assembly of the Molecular Catalysts in Nanoreactors 359 10.3.1 Incorporating Chiral Molecular Catalysts in Nanoreactors through Covalent-Bonding Methods 359 10.3.2 Immobilizing Chiral Molecular Catalysts in Nanoreactors through Noncovalent Bonding Methods 363 10.

4 Catalytic Reactions in Nanoreactors 369 10.4.1 Pore Confinement Effect 369 10.4.2 Enhanced Cooperative Activation Effect in Nanoreactors 377 10.4.3 Isolation Effect in Nanoreactors 382 10.4.

4 Microenvironment Engineering of Nanoreactors 385 10.4.5 Influence of the Porous Structure on the Catalytic Performance of Nanoreactors 388 10.4.6 Catalytic Nanoreactor Engineering 390 10.5 Conclusions and Perspectives 390 References 392 11 Heterogeneous Catalysis by Gold Clusters 397 Jiahui Huang and Masatake Haruta 11.1 Introduction 397 11.2 Preparation of Gold Clusters 399 11.

2.1 Chemical Reduction 399 11.2.2 Physical Vapor Deposition 403 11.2.3 Electrical Reduction 404 11.2.4 Other Methods 404 11.

3 Characterization of Gold Clusters 405 11.4 Catalysis by Gold Clusters.