Advances in Catalysis (eBook)

H. Knupffer (Herausgeber)

eBook Download: EPUB

2006 | 1. Auflage
326 Seiten
Elsevier Science (Verlag)
978-0-08-046218-9 (ISBN)

Infos

Catalysis is the acceleration of a chemical reaction by a catalyst, a substance that notably affects the rate of a chemical reaction without itself being consumed or altered. Since 1948, Advances in Catalysis has filled the gap between the papers that report on and the textbooks that teach in the diverse areas of catalysis research. The editors of and contributors to Advances in Catalysis are dedicated to recording progress in this area. Volume 49 reviews the directed evolution of enantioselective enzymes as catalysts for organic synthesis; dendrimers in catalysis and catalysis in ionic liquids; and the optimization of alkaline earth metal oxide and hydroxide catalysts for base-catalyzed reactions.

* Provides a comprehensive review of all aspects of catalytic research
* Contains in-depth, critical, state-of-the-art reports
* An indispensable source for researchers in academia and industry

Inhalt

Cover 1
copyright 5
Contents 6
front matter 12
Contributors 12
Preface 14
body 18
Directed Evolution of Enantioselective Enzymes as Catalysts for Organic Synthesis 18
Introduction 19
Mutagenesis Methods 22
Methods Based on Point Mutations 22
Recombinant Methods 24
High- and Medium-Throughput Screening Systems for Assaying the Enantioselectivity of Enzymatic Reactions 27
UV/Vis-Based EE Assays 28
Assay for Screening Lipases or Esterases in the Kinetic Resolution of Chiral p-Nitrophenyl Esters 28
Quick-E-Test in the Lipase- or Esterase-Catalyzed Kinetic Resolution of Chiral p-Nitrophenyl Esters 30
Screening Systems for Lipase- or Esterase-Catalyzed Reactions Based on pH-Indicators 31
Enzyme-Coupled ee Screening Systems 32
Other UV/Vis-Based ee Assays 34
Assays Using Fluorescence 35
Assays Based on Mass Spectrometry 37
Assays Based on NMR Spectroscopy 40
Assays Based on FTIR Spectroscopy for Assaying Lipases or Esterases 42
Assays Based on Gas Chromatography or HPLC 43
Assays Based on Capillary Array Electrophoresis 45
Assays Based on Circular Dichroism 45
Other ee Assays 47
Examples of Directed Evolution as a Means to Control the Enantioselectivity of Enzymes 47
Hydrolases 48
Lipase from Pseudomonas Aeruginosa 48
Other Lipases 58
Esterases 60
Epoxide Hydrolases 62
Hydantoinases 65
Nitrilases 66
Phosphotriesterases 68
Aminotransferases 69
Aldolases 69
Oxidases 71
Cyclohexanone Monooxygenases as Baeyer-Villigerases 72
Cyclohexanone Monooxygenases in Stereoselective Sulfoxidation 75
Monoamine Oxidases 76
Cytochrome P450 Enzymes 77
Conclusions and Perspective 78
References 79
Dendrimers in Catalysis 88
Introduction 88
Catalyst Recycling in Applications of Dendrimer-Supported Catalysts 92
Catalyst Recycling using Nanofiltration in a Continuous-Flow Membrane Reactor 92
Allylic Substitution using Dendritic Catalysts in a CFMR 92
Covalently Functionalized Dendrimers Applied in a CFMR 92
Non-covalently Functionalized Dendrimers Applied in a CFMR 99
Hydrovinylation using Dendritic Catalysts in a CFMR 100
Nickel-Catalyzed Kharasch Addition in a CFMR 102
Rhodium-Catalyzed Hydrogenation in a CFMR 103
Catalyst Recycling using Nanofiltration in Batch Processes 106
Acylation Reactions 106
Asymmetric Hydrogenation 108
Asymmetric Borohydride Reductions 109
Kharash Addition 110
Hydroformylation 112
Dendritic Catalyst Recycling by Precipitation 116
Heck and Sonogashira Reaction 117
Hydrogenation 118
Oxidation 119
Stille Couplings, Knoevenagel Condensations, and Michael Addition Reactions 121
Asymmetric Transfer Hydrogenation 124
Asymmetric Additions of Diethylzinc to Aldehydes 125
Catalyst Recovery by Column Chromatography 130
Metathesis 130
Asymmetric Dialkyl Zinc Addition 131
Recovery of Heterogeneous Dendritic Catalysts 132
Supported Dendritic Catalysts for Alkene Hydroformylation 132
Supported Dendritic Catalysts for Carbonylation, Hydroesterification, Oxidation, and Heck Reactions 137
Supported Dendritic Catalysts for the Asymmetric Addition of Diethylzinc 138
Scandium Cross-Linked Dendrimers as Lewis Acid Catalysts 141
Dendrimer-Bound Pd(II) Complex for Selective Hydrogenations 144
Dendrimers Supported on Montmorillonite 145
Dendritic Catalysts Applied in Two-Phase Catalysis 146
Water-Soluble Dendritic Catalysts for Alkene Hydroformylation 146
Dendrimer-Encapsulated Palladium Nanoparticles for Hydrogenations 147
Two-Phase Allylic Aminations and Heck Reactions using Thermomorphic Dendritic Catalysts 148
Dendritic Effects in Catalysis 150
Dendrimers as Soluble Supports 150
Dendrimers Supported on a Solid Phase 161
Conclusions 163
References 164
Catalysis in Ionic Liquids 170
Introduction 171
Ionic Liquids for Catalysis and Process Engineering 173
General Features of Ionic Liquids in Catalysis 173
Isolation of Catalysts 175
Product Separation and Catalyst Recycling 176
Structures and Properties of Ionic Liquids 177
Hydrogen Bond Basicity of Anions 178
Cations 180
Anions 181
Physical and Chemical Properties 183
Melting Point 183
Chloride-Containing Ionic Liquids 183
N-alkylpyridinium-Containing Ionic Liquids 184
N,N-dialkylpryrrolidinium-Containing Ionic Liquids 184
Alkylimidazolium-Containing Ionic Liquids 184
Quaternary Ammonium-Containing Ionic Liquids 186
AlCl3-Containing Ionic Liquids 186
Stability 187
Polarity 188
Viscosity 188
Solubility of Species in Ionic Liquids 189
Hydrogen 190
Oxygen 190
Carbon Monoxide 190
Carbon Dioxide and Lower Alkanes 191
Solubility of Organic Molecules 191
Solubilities of Catalysts 195
Brønsted Acidic Ionic Liquids 196
Basic Ionic Liquids 197
Impurities 198
Effect of Impurities 198
F. Impurity 198
Cl. Impurity 198
Ionic Liquids as Catalysts 199
Brønsted Acid Catalysis in Ionic Liquids 199
Lewis Acidic Ionic Liquids 201
Non-Chloroaluminate Lewis-Acid-Catalyzed Reactions 201
Friedel– Crafts Acylation 201
Diels– Alder Reactions 201
Chloroaluminate-Catalyzed Reactions 203
Alkylation 203
Dialkyl Ether Cleavage 204
Basic Ionic Liquids and Related Reactions 205
Aldol Reaction 205
Knoevenagel Condensation 206
Robinson Annulation 206
Neutral Ionic Liquids as Catalysts 207
Ionic Liquids as Catalyst Carriers 208
Characteristics of Ionic Liquid Catalyst Carriers 208
Inert Catalyst Carriers 208
Stabilization of Transition States 208
Lewis Acidity 209
Dispersion and Isolation of Organometallic Catalysts 211
Ligand Partitioning Effects 211
Ligand Effects of Ionic Liquids 213
Ionic Tagging of Active Catalysts 214
Hydrophobicity-Aided Catalysis 215
Enhanced Reaction Rate Due to Increased Substrate Solubility 215
Solubility-Aided Product Selectivity 216
Effect of Co-Solvents 218
Structural Effects of Cations 218
Reactivity of Proton at C2 Position in Imidazolium Ion 219
Phase Transfer Effect 219
Catalytic Reactions 220
Olefin Metathesis 221
Dimerization of Dienes 222
Olefin Dimerization 222
Suzuki Coupling 223
Hydrogenation 223
Oxidation 225
Dihydroxylation 226
Olefin Dimerization 227
Dimerization of Dienes 228
Oligomerization and Polymerization 229
Carbonylation/Hydroformylation 232
Heck Cross-Coupling 233
Alkoxycarbonylation 235
Cyclodehydration Reaction 235
Electrocatalysis in Ionic Liquids 236
Supported Ionic Liquid Catalysis 237
Biocatalysis in Ionic Liquid Media 240
Transesterification 241
Oxidation 244
Aldol Reactions 245
Galactosylation Reactions 245
Conclusions and Perspective 246
References 247
Optimization of Alkaline Earth Metal Oxide and Hydroxide Catalysts for Base-Catalyzed Reactions 256
Introduction 256
Surface Basicity and Base Strength of Alkaline Earth Metal Oxides 257
Synthesis of High-Surface-Area Alkaline Earth Metal Oxides 259
Characterization of the Number and Strength of Basic Sites 261
Titration Methods 262
Spectroscopic Methods 262
Infrared Spectroscopy of Adsorbed Probe Molecules 263
Thermal Methods of Adsorbed Probe Molecules 265
Catalytic Test Reactions 266
Knoevenagel Condensation 268
Acetonylacetone Cyclation 269
Isophorone Isomerization 270
Stability of Anionic Intermediates 270
Catalytic Activity of Alkaline Earth Metal Oxides 271
Isomerization Reactions 271
Carbon–Carbon Bond Formation Reactions 273
Aldol Condensations 273
Claisen-Schmidt Condensation 276
Nitroaldol Condensation 277
Knoevenagel Condensation 278
Wittig and Wittig– Horner Reactions 279
Michael Addition 280
Condensation of Alcohols 281
Carbon–Oxygen Bond Formation Reactions 282
Cyanoethylation of Alcohols 282
Conjugate Addition of Methanol to a, ß-unsaturated Carbonyl Compounds 283
Transesterification Reactions 283
Hydrogen Transfer Reactions 286
Tishchenko Reaction 286
Meerwein– Pondorff– Verley and Oppenauer Reactions 289
Zeolites and Mesoporous Aluminosilicates Modified with Alkaline Earth Metal Oxides 292
Catalytic Activities of Alkaline Earth-Modified Zeolites 294
Catalytic Activity of Alkaline Earth-Modified Mesoporous Molecular Sieves 296
Alkali Metal-Doped Alkaline Earth Metal Oxides 297
Methods of Preparation of Alkali Metal-Doped Alkaline Earth Metal Oxides 298
Alkaline Earth Metal Oxides Doped with Alkali Metals by Chemical Vapor Deposition 299
Alkaline Earth Metal Oxides Doped with Alkali Metals Prepared by Impregnation 301
Alkaline Earth Metal Hydroxides 304
Catalytic Reactions on Alkaline Earth Metal Hydroxides 306
Aldol Condensations 306
Claisen– Schmidt Condensation 306
Michael Additions 307
Wittig– Horner Reaction 308
Arylation of Carbonyl Compounds 310
Conclusions and Future Opportunities 311
Acknowledgment 312
References 312
Index 320

Produkt-Details

• Erscheint lt. Verlag: 10.2.2006
• Mitarbeit: Herausgeber (Serie): Bruce C. Gates
• Sprache: englisch
• Themenwelt: Sachbuch/Ratgeber
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Technische Chemie
• Themenwelt: Technik ► Umwelttechnik / Biotechnologie
• ISBN-10: 0-08-046218-9 / 0080462189
• ISBN-13: 978-0-08-046218-9 / 9780080462189