Metal-Catalyzed Reactions in Water -- Copyright Page -- Contents -- Preface -- List of Contributors -- 1 Metal-Catalyzed Cross-Couplings of Aryl Halides to Form C-C Bonds in Aqueous Media -- 1.1 Introduction -- 1.2 Aqueous-Phase Cross-Coupling Using Hydrophilic Catalysts -- 1.2.1 Hydrophilic Triarylphosphines and Diarylalkylphospines -- 1.2.2 Sterically Demanding, Hydrophilic Trialkyl and Dialkylbiarylphosphines -- 1.2.3 NHC Ligands -- 1.2.4 Nitrogen Ligands -- 1.2.5 Palladacyclic Complexes -- 1.3 Cross-Coupling in Aqueous Media Using Hydrophobic Ligands -- 1.3.1 Surfactant-Free Reactions -- 1.3.2 Surfactant-Promoted Reactions -- 1.3.2.1 Cationic Surfactants -- 1.3.2.2 Anionic Surfactants -- 1.3.2.3 Nonionic Surfactants -- 1.4 Heterogeneous Catalysts in Aqueous Media -- 1.4.1 Supported Palladium-Ligand Complexes -- 1.4.1.1 Polymer-Supported Palladium Complexes -- 1.4.1.2 Palladium Complexes Supported on Inorganic Materials -- 1.4.2 Nanoparticle-Catalyzed Coupling -- 1.4.2.1 Unsupported Palladium Nanoparticle Catalysts -- 1.4.2.2 Polymer-Supported Nanoparticles -- 1.4.2.3 Inorganic-Supported Nanoparticle Catalysts -- 1.5 Special Reaction Conditions -- 1.5.1 Microwave Heating -- 1.5.2 Ultrasound -- 1.5.3 Thermomorphic Reaction Control -- 1.6 Homogeneous Aqueous-Phase Modification of Biomolecules -- 1.6.1 Amino Acids and Proteins -- 1.6.2 Nucleosides and Nucleotides -- 1.7 Conclusion -- References -- 2 Metal-Catalyzed C-H Bond Activation and C-C Bond Formation in Water -- 2.1 Introduction -- 2.2 Catalytic Formation of C-C Bonds from spC-H Bonds in Water -- 2.2.1 Catalytic Nucleophilic Additions of Alkynes in Water -- 2.2.2 Addition of Terminal Alkynes to C-C Bonds in Water -- 2.2.3 The Sonogashira-Type Reactions in Water -- 2.3 Activation of sp2C-H Bonds for Catalytic C-C Bond Formation in Water -- 2.3.1 Homocoupling of sp2C-H Bonds.

2.3.2 Direct C-H Bond Arylation of Alkenes and Aryl Boronic Acid Derivatives -- 2.3.3 Cross-Coupling Reactions of sp2C-H Bonds with sp2C-X Bonds in Water -- 2.3.3.1 Direct C-H Bond Arylations with Aryl Halides and Palladium Catalysts -- 2.3.3.2 Direct C-H Bond Arylations with Aryl Halides and Ruthenium Catalysts -- 2.3.4 Cross-Coupling Reactions of sp2C-H Bonds with Carbon Nucleophiles in Water -- 2.3.5 Oxidative Cross-Coupling of sp2C-H Bond Reactions in Water -- 2.3.5.1 Alkenylations of Arenes and Heteroarenes with Palladium Catalysts -- 2.3.5.2 Alkenylation of Heterocycles Using In(OTf)3 Catalyst -- 2.3.5.3 Alkenylation of Arenes and Heteroarenes with Ruthenium(II) Catalysts -- 2.4 Activation of sp3C-H Bonds for Catalytic C-C Bond Formation in Water -- 2.4.1 Selective sp3C-H Activation of Ketones -- 2.4.2 Catalytic Enantioselective Alkynylation of sp3C-H Bonds -- 2.4.3 Cross-Dehydrogenative Coupling between sp3C-H Bonds Adjacent to a Heteroatom -- 2.4.4 Catalytic Enolate Carbon Coupling with (Arene) C-X Carbon -- 2.4.5 Arylation of sp3C-H Bonds with Aryl Halides or sp2C-H Bond -- 2.5 Conclusion -- Acknowledgments -- References -- 3 Catalytic Nucleophilic Additions of Alkynes in Water -- 3.1 Introduction -- 3.2 Catalytic Nucleophilic Additions of Terminal Alkynes with Carbonyl Derivatives -- 3.2.1 Reaction with Acid Chlorides -- 3.2.2 Reaction with Aldehydes -- 3.2.3 Reaction with Ketones -- 3.3 Addition of Terminal Alkyne to Imine, Tosylimine, Iminium Ion, and Acyl Iminium Ion -- 3.3.1 Reaction with Imines -- 3.3.2 Reaction with Iminium Ions -- 3.3.3 Reaction with Acylimine and Acyliminium Ions -- 3.4 Direct Conjugate Addition of Terminal Alkynes -- 3.5 Conclusions -- Acknowledgments -- References -- 4 Water-Soluble Hydroformylation Catalysis -- 4.1 Introduction -- 4.2 Hydroformylation of Light C2-C5 Alkenes in the RCH/RP Process.

4.3 Hydroformylation of Alkenes Heavier than C5 -- 4.3.1 Water-Soluble and Amphiphilic Ligands -- 4.3.2 Phase-Transfer Agents: Cyclodextrins and Calixarenes -- 4.3.3 Supported Aqueous-Phase Catalysis -- 4.4 Innovative Expansions -- 4.4.1 Thermoregulated Catalytic Systems -- 4.4.2 Ionic Liquids and Carbon Dioxide Induced Phase Switching -- 4.4.3 Cascade Reactions -- 4.5 Conclusion -- References -- 5 Green Catalytic Oxidations in Water -- 5.1 Introduction -- 5.2 Examples of Water-Soluble Ligands -- 5.3 Enzymatic Oxidations -- 5.4 Biomimetic Oxidations -- 5.5 Epoxidation, Dihydroxylation, and Oxidative Cleavage of Olefins -- 5.5.1 Tungsten-Based Systems -- 5.5.2 Manganese- and Iron-Based Systems -- 5.5.3 Ruthenium and Platinum Catalysts -- 5.5.4 Other Systems -- 5.6 Alcohol Oxidations -- 5.6.1 Tungsten (VI) Catalysts -- 5.6.2 Palladium Diamine Complexes as Catalysts -- 5.6.3 Noble Metal Nanoparticles as Quasi-Homogeneous Catalysts -- 5.6.4 Ruthenium and Manganese Catalysts -- 5.6.5 Organocatalysts: Stable N-Oxy Radicals and Hypervalent Iodine Compounds -- 5.6.6 Enzymatic Oxidation of Alcohols -- 5.7 Sulfoxidations in Water -- 5.7.1 Tungsten- and Vanadium-Catalyzed Oxidations -- 5.7.2 Enantioselective Sulfoxidation with Enzymes -- 5.7.3 Flavins as Organocatalysts for Sulfoxidation -- 5.8 Conclusions and Future Outlook -- References -- 6 Hydrogenation and Transfer Hydrogenation in Water -- 6.1 Introduction -- 6.2 Water-Soluble Ligands -- 6.2.1 Water-Soluble Achiral Ligands -- 6.2.2 Water-Soluble Chiral Ligands -- 6.3 Hydrogenation in Water -- 6.3.1 Achiral Hydrogenation -- 6.3.1.1 Hydrogenation of Olefins -- 6.3.1.2 Hydrogenation of Carbonyl Compounds -- 6.3.1.3 Hydrogenation of Aromatic Rings -- 6.3.1.4 Hydrogenation of Other Organic Groups -- 6.3.1.5 Hydrogenation of CO2 -- 6.3.2 Asymmetric Hydrogenation -- 6.3.2.1 Asymmetric Hydrogenation of Olefins.

6.3.2.2 Asymmetric Hydrogenation of Carbonyl and Related Compounds -- 6.3.2.3 Asymmetric Hydrogenation of Imines -- 6.4 Transfer Hydrogenation in Water -- 6.4.1 Achiral Transfer Hydrogenation -- 6.4.1.1 Achiral Transfer Hydrogenation of Carbonyl Compounds -- 6.4.1.2 Achiral Transfer Hydrogenation of Imino Compounds -- 6.4.2 Asymmetric Transfer Hydrogenation -- 6.4.2.1 Asymmetric Transfer Hydrogenation of C=C Double Bonds -- 6.4.2.2 Asymmetric Transfer Hydrogenation of Simple Ketones -- 6.4.2.3 Asymmetric Transfer Hydrogenation of Functionalized Ketones -- 6.4.2.4 Asymmetric Transfer Hydrogenation of Imines -- 6.4.3 Asymmetric Transfer Hydrogenation with Biomimetic Catalysts -- 6.4.4 Asymmetric Transfer Hydrogenation with Immobilized Catalysts -- 6.5 Role of Water -- 6.5.1 Coordination to Metals -- 6.5.2 Acid-Base Equilibrium -- 6.5.3 H-D Exchange -- 6.5.4 Participation in Transition States -- 6.6 Concluding Remarks -- References -- 7 Catalytic Rearrangements and Allylation Reactions in Water -- 7.1 Introduction -- 7.2 Rearrangements -- 7.2.1 Isomerization of Olefinic Substrates -- 7.2.1.1 Isomerization of Allylic Alcohols, Ethers, and Amines -- 7.2.1.2 Isomerization of Other Olefins -- 7.2.2 Cycloisomerizations and Related Cyclization Processes -- 7.2.3 Other Rearrangements -- 7.3 Allylation Reactions -- 7.3.1 Allylic Substitution Reactions -- 7.3.1.1 Palladium-Catalyzed Allylic Substitution Reactions (Tsuji-Trost Allylations) -- 7.3.1.2 Other Metal-Catalyzed Allylic Substitution Reactions -- 7.3.2 Allylation Reactions of C=O and C=N Bonds -- 7.3.3 Other Allylation Reactions in Aqueous Media -- 7.4 Conclusion -- Acknowledgments -- References -- 8 Alkene Metathesis in Water -- 8.1 Introduction -- 8.1.1 General Introduction to Olefin Metathesis -- 8.1.2 Metathesis of Water-Soluble Substrates -- 8.1.3 Metathesis of Water-Insoluble Substrates.

8.1.3.1 "Enabling Techniques" for Olefin Metathesis in Aqueous Media -- 8.1.3.2 Other Additives and Techniques -- 8.2 Examples of Applications of Olefin Metathesis in Aqueous Media -- 8.2.1 Polymerizations -- 8.2.2 Metathesis of Water-Soluble Substrates -- 8.2.2.1 Ring-Closing Metathesis and Enyne Cycloisomerization of Water-Soluble Substrates -- 8.2.2.2 Cross Metathesis of Water-Soluble Substrates -- 8.2.3 Cross Metathesis with Substrate Having an Allylic Heteroatom -- 8.2.4 Metathesis of Water-Insoluble Substrates -- 8.2.4.1 Ring-Closing Metathesis of Water-Insoluble Substrates -- 8.2.4.2 Enyne Cycloisomerization -- 8.2.4.3 Cross Metathesis of Water-Insoluble Substrates -- 8.3 Conclusions and Outlook -- Acknowledgments -- References -- 9 Nanocatalysis in Water -- 9.1 Introduction -- 9.2 Nanocatalysis -- 9.3 Effects of Size of Nanocatalysts -- 9.4 Transition-Metal Nanoparticles -- 9.4.1 Synthesis of Transition-Metal Nanoparticles -- 9.4.2 Greener Synthesis of Nanomaterials -- 9.4.3 Immobilization of M-NPs on a Solid Support -- 9.5 Catalytic Applications of Transition-Metal-Based Nanomaterials -- 9.6 Pd Nanoparticles in Organic Synthesis -- 9.6.1 Pd Nanoparticles in Suzuki Reactions -- 9.6.2 Pd Nanoparticles in the Heck Reactions -- 9.6.3 Pd Nanoparticles in the Sonogashira Reactions -- 9.6.4 Pd Nanoparticles in the Stille Coupling Reactions -- 9.6.5 Pd Nanoparticles in the Hiyama Couplings -- 9.6.6 Pd Nanoparticles in the Tsuji-Trost Reaction -- 9.7 Nanogold Catalysis -- 9.7.1 Coupling Reactions -- 9.7.1.1 The Suzuki-Miyaura Cross-Coupling Reaction -- 9.7.1.2 Homocoupling of Arylboronic Acid -- 9.7.2 Reduction Reactions -- 9.7.2.1 Hydrogenation of Benzene -- 9.7.2.2 Nitro group reduction -- 9.7.3 Oxidation Reactions -- 9.7.3.1 Benzylic and Allylic C-H Bonds Oxidation -- 9.7.3.2 Epoxidation of Propylene -- 9.7.3.3 Oxidation of Alcohols.

9.7.4 Hydration of Alkynes.