内容

目次

Preface. Foreword. 1 Introduction: Green Chemistry and Catalysis.1.1 Introduction. 1.2. E Factors and Atom Efficiency. 1.3 The Role ofCatalysis. 1.4 The Development of Organic Synthesis. 1.5 Catalysis bySolid Acids and Bases. 1.6 Catalytic Reduction. 1.7 CatalyticOxidation. 1.8 Catalytic C-C Bond Formation. 1.9 The Question ofSolvents: Alternative Reaction Media. 1.10 Biocatalysis. 1.11 RenewableRaw Materials and White Biotechnology. 1.12 Enantioselective Catalysis.1.13 Risky Reagents. 1.14 Process Integration and Catalytic Cascades.References. 2 Solid Acids and Bases as Catalysts. 2.1 Introduction.2.2 Solid Acid Catalysis. 2.2.1 Acidic Clays. 2.2.2 Zeolites andZeotypes: Synthesis and Structure. 2.2.3 Zeolite-catalyzed Reactions inOrganic Synthesis. 2.2.3.1 Electrophilic Aromatic Substitutions.2.2.3.2 Additions and Eliminations. 2.2.3.3 Rearrangements andIsomerizations. 2.2.3.4 Cyclizations. 2.2.4 Solid Acids ContainingSurface SO3H Functionality. 2.2.5 Heteropoly Acids. 2.3 Solid BaseCatalysis. 2.3.1 Anionic Clays: Hydrotalcites. 2.3.2 Basic Zeolites.2.3.3 Organic Bases Attached to Mesoporous Silicas. 2.4 Other Approaches.References. 3 Catalytic Reductions. 3.1 Introduction. 3.2Heterogeneous Reduction Catalysts. 3.2.1 General Properties. 3.2.2Transfer Hydrogenation Using Heterogeneous Catalysts. 3.2.3 ChiralHeterogeneous Reduction Catalysts. 3.3 Homogeneous Reduction Catalysts.3.3.1 Wilkinson Catalyst. 3.3.2 Chiral Homogeneous Hydrogenation Catalystsand Reduction of the C= C Double Bond. 3.3.3 Chiral Homogeneous Catalystsand Ketone Hydrogenation. 3.3.4 Imine Hydrogenation. 3.3.5 TransferHydrogenation using Homogeneous Catalysts. 3.4 Biocatalytic Reductions.3.4.1 Introduction. 3.4.2 Enzyme Technology in Biocatalytic Reduction.3.4.3 Whole Cell Technology for Biocatalytic Reduction. 3.5 Conclusions.References. 4 Catalytic Oxidations. 4.1 Introduction. 4.2Mechanisms of Metal-catalyzed Oxidations: General Considerations. 4.2.1Homolytic Mechanisms. 4.2.1.1 Direct Homolytic Oxidation of OrganicSubstrates. 4.2.2 Heterolytic Mechanisms. 4.2.2.1 Catalytic OxygenTransfer. 4.2.3 Ligand Design in Oxidation Catalysis. 4.2.4 EnzymeCatalyzed Oxidations. 4.3 Alkenes. 4.3.1 Epoxidation. 4.3.1.1Tungsten Catalysts. 4.3.1.2 Rhenium Catalysts. 4.3.1.3 RutheniumCatalysts. 4.3.1.4 Manganese Catalysts. 4.3.1.5 Iron Catalysts.4.3.1.6 Selenium and Organocatalysts. 4.3.1.7 Hydrotalcite and AluminaSystems. 4.3.1.8 Biocatalytic Systems. 4.3.2 Vicinal Dihydroxylation.4.3.3 Oxidative Cleavage of Olefins. 4.3.4 Oxidative Ketonization.4.3.5 Allylic Oxidations. 4.4 Alkanes and Alkylaromatics. 4.4.1Oxidation of Alkanes. 4.4.2 Oxidation of Aromatic Side Chains. 4.4.3Aromatic Ring Oxidation. 4.5 Oxygen-containing Compounds. 4.5.1Oxidation of Alcohols. 4.5.1.1 Ruthenium Catalysts. 4.5.1.2Palladium-catalyzed Oxidations with O<sub>2</sub>. 4.5.1.3Gold Catalysts. 4.5.1.4 Copper Catalysts. 4.5.1.5 Other Metals asCatalysts for Oxidation with O<sub>2</sub>. 4.5.1.6 CatalyticOxidation of Alcohols with Hydrogen Peroxide. 4.5.1.7 Oxoammonium Ions inAlcohol Oxidation. 4.5.1.8 Biocatalytic Oxidation of Alcohols. 4.5.2Oxidative Cleavage of 1,2-Diols. 4.5.3 Carbohydrate Oxidation. 4.5.4Oxidation of Aldehydes and Ketones. 4.5.4.1 Baeyer-Villiger Oxidation.4.5.5 Oxidation of Phenols. 4.5.6 Oxidation of Ethers. 4.6 HeteroatomOxidation. 4.6.1 Oxidation of Amines. 4.6.1.1 Primary Amines.4.6.1.2 Secondary Amines. 4.6.1.3 Tertiary Amines. 4.6.1.4 Amides.4.6.2 Sulfoxidation. 4.7 Asymmetric Oxidation. 4.7.1 AsymmetricEpoxidation of Olefins. 4.7.2 Asymmetric Dihydroxylation of Olefins.4.7.3 Asymmetric Sulfoxidation. 4.7.4 Asymmetric Baeyer-VilligerOxidation. 4.5 Conclusion. References. 5 Catalytic Carbon-CarbonBond Formation. 5.1 Introduction. 5.2 Enzymes for Carbon-Carbon BondFormation. 5.2.1 Enzymatic Synthesis of Cyanohydrins. 5.2.1.1Hydroxynitrile Lyases. 5.2.1.2 Lipase-based Dynamic Kinetic Resolution.5.2.2 Enzymatic Synthesis of α-Hydroxyketones (Acyloins). 5.2.3Enzymatic Synthesis of α-Hydroxy Acids. 5.2.4 EnzymaticSynthesis of Aldols (β-Hydroxy Carbonyl Compounds). 5.2.4.1DHAP-dependent Aldolases. 5.2.4.2 PEP- and Pyruvate-dependent Aldolases.5.2.4.3 Glycine-dependent Aldolases. 5.2.4.4 Acetaldehyde-dependentAldolases. 5.2.5 Enzymatic Synthesis of β-Hydroxynitriles. 5.3Transition Metal Catalysis. 5.3.1 Carbon Monoxide as a Building Block.5.3.1.1 Carbonylation of R-X (CO "Insertion/R-migration"). 5.3.1.2Aminocarbonylation. 5.3.1.3 Hydroformylation or "Oxo" Reaction. 5.3.1.4Hydroaminomethylation. 5.3.1.5 Methyl Methacrylate via CarbonylationReactions. 5.3.2 Heck-type Reactions. 5.3.2.1 Heck Reaction. 5.3.2.2Suzuki and Sonogashira Reaction. 5.3.3 Metathesis. 5.3.3.1 Metathesisinvolving Propylene. 5.3.3.2 Ring-opening Metathesis Polymerization(ROMP). 5.3.3.3 Ring-closing Metathesis (RCM). 5.4 Conclusion andOutlook. References. 6 Hydrolysis. 6.1 Introduction. 6.1.1Stereoselectivity of Hydrolases. 6.1.2 Hydrolase-based Preparation ofEnantiopure Compounds. 6.1.2.1 Kinetic Resolutions. 6.1.2.2 DynamicKinetic Resolutions. 6.1.2.3 Kinetic Resolutions Combined with Inversions.6.1.2.4 Hydrolysis of Symmetric Molecules and the "meso-trick." 6.2Hydrolysis of Esters. 6.2.1 Kinetic Resolutions of Esters. 6.2.2Dynamic Kinetic Resolutions of Esters. 6.2.3 Kinetic Resolutions of EstersCombined with Inversions. 6.2.4 Hydrolysis of Symmetric Esters and the"meso-trick." 6.3 Hydrolysis of Amides. 6.3.1 Production of Amino Acidsby (Dynamic) Kinetic Resolution. 6.3.1.1 The Acylase Process. 6.3.1.2The Amidase Process. 6.3.1.3 The Hydantoinase Process. 6.3.1.4Cysteine. 6.3.2 Enzyme-catalysed Hydrolysis of Amides. 6.3.3Enzyme-catalysed Deprotection of Amines. 6.4 Hydrolysis of Nitriles.6.4.1 Nitrilases. 6.4.2 Nitrile Hydratases. 6.5 Conclusion and Outlook.References. 7 Catalysis in Novel Reaction Media. 7.1 Introduction.7.1.1 Why use a solvent? 7.1.2 Choice of Solvent. 7.1.3 AlternativeReaction Media and Multiphasic Systems. 7.2 Two Immiscible OrganicSolvents. 7.3 Aqueous Biphasic Catalysis. 7.3.1 OlefinHydroformylation. 7.3.2 Hydrogenation. 7.3.3 Carbonylations. 7.3.4Other C-C Bond Forming Reactions. 7.3.5 Oxidations. 7.4 FluorousBiphasic Catalysis. 7.4.1 Olefin Hydroformylation. 7.4.2 OtherReactions. 7.5 Supercritical Carbon Dioxide. 7.5.1 SupercriticalFluids. 7.5.2 Supercritical Carbon Dioxide. 7.5.3 Hydrogenation.7.5.4 Oxidation. 7.5.5 Biocatalysis. 7.6 Ionic Liquids. 7.7 BiphasicSystems with Supercritical Carbon Dioxide. 7.8 Thermoregulated BiphasicCatalysis. 7.9 Conclusions and Prospects. References. 8 Chemicalsfrom Renewable Raw Materials. 8.1 Introduction. 8.2 Carbohydrates.8.2.1 Chemicals from Glucose via Fermentation. 8.2.2 Ethanol. 8.2.2.1Microbial Production of Ethanol. 8.2.2.2 Green Aspects. 8.2.3 LacticAcid. 8.2.4 1,3-Propanediol. 8.2.5 3-Hydroxypropanoic Acid. 8.2.6Synthesizing Aromatics in Nature's Way. 8.2.7 Aromatic -Amino Acids.8.2.7 Indigo: the Natural Color. 8.2.8 Pantothenic Acid. 8.2.9 Theβ-Lactam Building Block 7-Aminodesacetoxycephalosporanic Acid.8.2.9 Riboflavin. 8.3 Chemical and Chemoenzymatic Transformations ofCarbohydrates into Fine Chemicals and Chiral Building Blocks. 8.3.1Ascorbic Acid. 8.3.2 Carbohydrate-derived C3 and C4 Building Blocks.8.3.3 5-Hydroxymethylfurfural and Levulinic Acid. 8.4 Fats and Oils.8.4.1 Biodiesel. 8.4.2 Fatty Acid Esters. 8.5 Terpenes. 8.6Renewable Raw Materials as Catalysts. 8.7 Green Polymers from RenewableRaw Materials. 8.8 Concluding Remarks. References. 9 ProcessIntegration and Cascade Catalysis. 9.1 Introduction. 9.2 DynamicKinetic Resolutions by Enzymes Coupled with Metal Catalysts. 9.3Combination of Asymmetric Hydrogenation with Enzymatic Hydrolysis. 9.4Catalyst Recovery and Recycling. 9.5 Immobilization of Enzymes:Cross-linked Enzyme Aggregates (CLEAs). 9.6 Conclusions and Prospects.References. 10 Epilogue: Future Outlook. 10.1 Green Chemistry: The Roadto Sustainability. 10.2 Catalysis and Green Chemistry. 10.3 The Mediumis the Message. 10.4 Metabolic Engineering and Cascade Catalysis. 10.5Concluding Remarks. References. Subject Index.