Palladium-Catalyzed Coupling Reactions: Practical Aspects and Future Developments -- Contents -- Foreword -- Preface -- List of Contributors -- 1 Palladium-Catalyzed Cross-Coupling Reactions - A General Introduction -- 1.1 Introduction -- 1.1.1 Historical Reflection -- 1.1.2 Characteristics, Recent Developments, and Progress -- 1.1.3 Literature Reviews and Organization of the Chapter -- 1.2 Carbon-Carbon Cross-Coupling Reactions Catalyzed by Palladium -- 1.2.1 Classification and Overview -- 1.2.2 Common Mechanistic Features of Cross-Coupling Reactions and Reactivity of the Substrates -- 1.2.2.1 Choice of the Carbon Electrophile -- 1.2.2.2 Choice of the Carbon Nucleophile - What Makes the Difference? -- 1.3 The Catalysts -- 1.3.1 The Particular Features of Palladium -- 1.3.2 Classes of Palladium Catalysts Applied to Cross-Coupling Reactions -- 1.3.2.1 Ligands and Palladium Complexes - Homogeneous Systems -- 1.3.2.2 Immobilized or Supported Palladium Complexes and Particles - Heterogeneous Systems -- 1.3.2.3 Palladium Colloids and (Nonsupported) Nanoparticles -- 1.3.2.4 Activity of Heterogeneous Catalysts -- 1.4 Mechanistic Aspects -- 1.4.1 General Mechanism of C C Cross-Coupling and Heck Reactions with Homogeneous Catalyst Precursors -- 1.4.2 Models for Heck and Suzuki Reactions with Supported Pd Precursors -- 1.4.3 Recent Results on the Reaction Mechanism and the Nature of the Active Pd Species -- 1.4.3.1 Observation of Intermediates in Homogeneous Catalysis by Electrochemical Methods -- 1.4.3.2 The Question of Pd Leaching -- 1.4.3.3 Selectivity Pattern -- 1.4.3.4 In Situ Observation by Spectroscopic Methods -- 1.4.3.5 Immobilized Pd Pincer Complexes -- 1.4.3.6 Palladium Bulk Materials (Pd Foil, Wire, Sponge) as Catalyst -- 1.5 Future Challenges -- Abbreviations -- References.

2 High-Turnover Heterogeneous Palladium Catalysts in Coupling Reactions: the Case of Pd Loaded on Dealuminated Y Zeolites -- 2.1 Introduction -- 2.2 Various Methodologies to Afford High Turnover Numbers Over Supported Pd Catalysts -- 2.3 Structure and Characteristics of Ultrastable Y Zeolites -- 2.4 Suzuki-Miyaura Reactions Catalyzed by Pd/USY -- 2.4.1 Catalytic Performance of Pd/USY -- 2.4.2 Pd Leaching from Pd/USY -- 2.4.3 Selectivity in the Homocoupling Reactions -- 2.4.4 Characterization of the Active Pd Species by X-Ray Absorption Spectroscopy -- 2.4.5 A Suggested Mechanism for the Formation of Active Pd Species in Suzuki-Miyaura Coupling Reactions -- 2.5 Catalytic Performance of Pd/USY in Mizoroki-Heck Reactions -- 2.5.1 Effect of H2 Bubbling on the Catalytic Reactions of Pd/USY -- 2.5.2 Catalytic Reactions Using Chlorobenzene Derivatives -- 2.5.3 Characterization of the Pd Species by X-Ray Absorption Spectroscopy -- 2.6 Conclusion and Perspective -- Abbreviations -- References -- 3 Palladium-Catalyzed Coupling Reactions with Magnetically Separable Nanocatalysts -- 3.1 Introduction -- 3.2 General Considerations Concerning Magnetic Particles as Catalyst Supports -- 3.3 Palladium Nanoparticles on Magnetic Supports -- 3.4 Molecular Palladium Complexes on Magnetic Supports -- 3.5 Outlook -- Abbreviations -- References -- 4 The Use of Ordered Porous Solids as Support Materials in Palladium-Catalyzed Cross-Coupling Reactions -- 4.1 Introduction -- 4.2 Catalyst Synthesis and Characterization -- 4.3 Carbon-Carbon Couplings -- 4.3.1 Zeolites -- 4.3.2 Mesoporous Ordered Silica Materials -- 4.3.2.1 Coupling Reactions Catalyzed by Supported Palladium Particles -- 4.3.2.2 Reactions Mediated by Immobilized Palladium Species -- 4.3.3 Periodic Mesoporous Organosilicas -- 4.3.4 Catalysts Based on Nonsiliceous Solids -- 4.3.4.1 Metal-Organic Frameworks.

4.3.4.2 Covalent Organic Frameworks -- 4.3.4.3 Other Support Materials -- 4.4 Miscellaneous Coupling Reactions -- 4.5 The Question of Solution-Phase Catalysis -- 4.6 Summary and Future Prospects -- Abbreviations -- References -- 5 Coupling Reactions Induced by Polymer-Supported Catalysts -- 5.1 Introduction -- 5.2 Polysaccharides -- 5.2.1 Starch -- 5.2.2 Chitosan -- 5.2.3 Other Polysaccharides -- 5.3 Poly(ethylene glycol) -- 5.3.1 Nonfunctionalized Poly(ethylene glycol) -- 5.3.2 Functionalized Poly(ethylene glycol) -- 5.4 Polystyrene -- 5.4.1 Nonfunctionalized Polystyrene -- 5.4.2 Functionalized Polystyrene -- 5.4.2.1 Polystyrene-Supported Ligands Containing Nitrogen -- 5.4.2.2 Polystyrene-Supported Triphenylphosphane -- 5.5 Poly(norbornene) -- 5.6 Polyacrylamide -- 5.7 Polyaniline -- 5.8 Poly(N-vinyl-2-pyrrolidone) -- 5.9 Polypyrrole -- 5.10 Poly(4-vinylpyridine) -- 5.11 Ionic Polymers -- 5.11.1 Organic Polymers Containing N-Heterocyclic Carbenes or Ionic Liquids -- 5.11.2 Polymers Containing Other Ionic Ligands -- 5.12 Organometallic Polymers -- 5.13 Functionalized Porous Organic Polymers -- 5.14 Miscellaneous Polymers -- 5.15 Summary and Outlook -- Abbreviations -- References -- 6 Coupling Reactions in Ionic Liquids -- 6.1 Introduction -- 6.2 Metal Complexes -- 6.2.1 Mizoroki-Heck Reaction -- 6.2.2 Sonogashira Coupling -- 6.2.3 Suzuki-Miyaura Coupling -- 6.2.4 Negishi Coupling -- 6.2.5 Trost-Tsuji Coupling -- 6.3 Metal Salts and Metal on Solid Support -- 6.3.1 Mizoroki-Heck Reaction -- 6.3.2 Suzuki-Miyaura Reaction -- 6.3.3 Stille Reaction -- 6.4 Metal Nanoparticles -- 6.4.1 The Mizoroki-Heck Reaction with PdNPs in ILs -- 6.4.2 Suzuki-Miyaura Reaction -- 6.4.3 Stille Reaction -- 6.4.4 Buchwald-Hartwig Reaction -- 6.4.5 Sonogashira Reaction -- 6.4.6 Ullmann Reaction -- 6.5 Summary and Outlook -- Abbreviations -- References.

7 Cross-Coupling Reactions in Aqueous Media -- 7.1 Introduction -- 7.2 Cross-Coupling of Organic Halides to Form C-C Bonds in Aqueous Media -- 7.2.1 Suzuki Coupling -- 7.2.1.1 Aqueous-Phase Suzuki Coupling Using Hydrophilic Ligand-Supported Catalysts -- 7.2.1.2 On Water Suzuki Couplings with Hydrophobic Catalyst Systems -- 7.2.1.3 Surfactant-Promoted Aqueous-Phase Suzuki Couplings -- 7.2.1.4 Palladium Catalysts Supported on Heterogeneous Supports -- 7.2.1.5 Palladium Nanoparticle Catalysts -- 7.2.2 Stille Coupling -- 7.2.3 Hiyama Coupling -- 7.2.4 Negishi Coupling -- 7.2.5 Sonogashira Coupling -- 7.2.6 Arylation of Other Carbanion Nucleophiles -- 7.2.7 Heck Coupling -- 7.3 Carbon-Heteroatom Coupling Reactions -- 7.3.1 Amination of Aryl Halides -- 7.3.2 Other Carbon-Heteroatom Coupling Reactions -- 7.4 C-H Activation in Aqueous Media -- 7.5 Conclusion and Future Prospects -- Abbreviations -- References -- 8 Microwave-Assisted Synthesis in C-C and Carbon-Heteroatom Coupling Reactions -- 8.1 Introduction -- 8.2 C-C Bond Formation -- 8.2.1 Heck Coupling Reactions -- 8.2.2 Suzuki Reactions -- 8.2.3 Negishi Couplings -- 8.2.4 Coupling of Terminal Alkynes with Aryl Halides -- 8.2.5 Coupling Reactions of Organostannanes with Organic Halides -- 8.2.6 Couplings of Organosilanes with Aryl Halides -- 8.2.7 Cyanation of Aryl Halides -- 8.2.8 Carbonylation Reactions -- 8.2.9 Decarboxylative Couplings -- 8.2.10 Other C-C Bond Formations -- 8.3 C-X Bond Formation -- 8.3.1 C-N Bond Formation -- 8.3.2 C-P Bond Formation -- 8.4 Conclusions -- Abbreviations -- References -- 9 Catalyst Recycling in Palladium-Catalyzed Carbon-Carbon Coupling Reactions -- 9.1 Introduction -- 9.2 General Issues of Catalyst Recycling -- 9.3 Catalyst Systems Providing High, Consistent Yields in Recycling -- 9.3.1 The Use of Catalysts with Pd Particles -- 9.3.2 Recycling of Palladium Complexes.

9.3.2.1 Complexes Anchored to Inorganic Supports -- 9.3.2.2 Complexes Immobilized on Polymers -- 9.3.2.3 Self-Supported Polymeric Complexes -- 9.3.3 Studies Performed Under Homogeneous Conditions -- 9.4 Catalysts Affording the Highest Cumulative TON Values in Recycling Studies -- 9.4.1 Catalysts with Supported Particles -- 9.4.2 Immobilized Complexes -- 9.5 Summary Evaluation -- 9.6 Future Outlook -- Abbreviations -- References -- 10 Nature of the True Catalytic Species in Carbon-Carbon Coupling Reactions with Heterogeneous Palladium Precatalysts -- 10.1 Introduction -- 10.2 Heck Reactions -- 10.2.1 Supported Pd Particles -- 10.2.2 Immobilized Pd Complexes -- 10.3 Suzuki Reactions -- 10.3.1 Supported Pd Particles -- 10.3.2 Immobilized Pd Complexes -- 10.4 Sonogashira Reactions -- 10.4.1 Supported Pd Particles -- 10.4.2 Immobilized Pd Complexes -- 10.5 Concluding Remarks -- Abbreviations -- References -- 11 Coupling Reactions in Continuous-Flow Systems -- 11.1 Introduction -- 11.2 Coupling Reactions in Flow -- 11.2.1 Suzuki-Miyaura Coupling -- 11.2.2 Mizoroki-Heck Coupling -- 11.2.3 Sonogashira Coupling -- 11.2.4 Murahashi Coupling -- 11.2.5 Hiyama Coupling -- 11.2.6 Carbonylative Couplings -- 11.2.7 Buchwald-Hartwig Amination -- 11.3 Palladium Catalysts for Flow Systems -- 11.3.1 Heterogeneous Supported Catalysts -- 11.3.1.1 Palladium on Charcoal -- 11.3.1.2 Pd EnCat -- 11.3.1.3 Silicon Dioxide Supports -- 11.3.1.4 Polymeric Supports -- 11.3.1.5 Magnetic Nanoparticles -- 11.3.1.6 Monolithic Supports -- 11.3.2 Homogeneous Catalysts -- 11.3.2.1 Single-Phase Reactions -- 11.3.2.2 Biphasic Systems -- 11.4 Continuous-Flow Technologies for Cross-Coupling -- 11.4.1 Microreactors -- 11.4.2 Microwave-Assisted Continuous-Flow Organic Synthesis -- 11.4.3 Toward Sequential Coupling Reactions in Flow -- 11.5 Summary and Outlook -- Abbreviations -- References.

12 Palladium-Catalyzed Cross-Coupling Reactions - Industrial Applications.