Bimetallic Catalysts In Organic Synthesis

Description:
This first book to comprehensively cover this hot topic presents the information hitherto scattered throughout smaller reviews or single book chapters to provide an introduction to this rapidly expanding field. In ten chapters, the international team of expert authors treats asymmetric syntheses, new transformations, and organometallic reactions using homo-- and hetero--bimetallic catalysts. Written for advanced researchers, this very timely publication is of significant benefit to organic and organometallic chemists in both academia and industry.

Table of Contents:
Preface.List of Contributors.1 Organic Synthesis with Bimetallic Systems (Shin Kamijo and Yoshinori Yamamoto).1.1 Introduction.1.2 Reactions Promoted by a Combination of Catalytic and Stoichiometric Amounts of Metals.1.2.1 Transition Metal-Catalyzed Cross-Coupling Reactions.1.2.2 The Wacker Reaction.1.2.3 The Heck Reaction.1.2.4 Reactions Involving pi-Allylpalladium Intermediates.1.2.4.1 Electrophilic Reactions.1.2.4.2 Nucleophilic Reactions.1.2.5 Nickel-Catalyzed Three-Component Coupling Reaction.1.2.6 The Nozaki-Hiyama-Kishi Reaction.1.3 Reactions Promoted by a Combination of Catalytic Amounts of Two Metals.1.3.1 Transition Metal Catalyzed Cross-Coupling Reactions.1.3.1.1 The Stille Reaction.1.3.1.2 The Hiyama Reaction.1.3.1.3 The Sonogashira Reaction.1.3.2 The Wacker Reaction.1.3.3 Reactions Involving eth-Allylpalladium Intermediates.1.3.4 Transition Metal Catalyzed Cyclization Reactions.1.3.4.1 [3+2] Cycloaddition Reactions.1.3.4.2 Intramolecular [n+2] Cyclization Reactions.1.3.4.3 Intermolecular [n+2+2] Cyclotrimerization Reactions.1.3.4.4 [2+2+1] Cycloaddition Reactions; The Pauson-Khand Reaction.1.3.4.5 Cycloisomerization Reactions.1.3.4.6 Indole-Forming Reaction.1.3.4.7 Furan- and Pyrrole-Forming Reactions.1.3.5 Reactions Involving Nucleophilic Addition of Carbonyl Compounds.1.3.5.1 The Aldol Reaction.1.3.5.2 Alkynylation Reactions.1.3.5.3 Conjugate Addition Reactions.1.3.6 Miscellaneous Reactions.1.3.6.1 Transition Metal Catalyzed Reactions.1.3.6.2 Lewis Acid Catalyzed Reactions.1.3.6.3 Sequential Reactions.References.2 Zinc Polymetallic Asymmetric Catalysis (Naoya Kumagai and Masakatsu Shibasaki).2.1 Introduction.2.2 Asymmetric Alternating Copolymerization with Dimeric Zn Complexes.2.3 Direct Catalytic Asymmetric Aldol Reaction with Zn Polymetallic Catalysts.2.3.1 Introduction.2.3.2 Direct Catalytic Asymmetric Aldol Reaction with Methyl Ketones.2.3.3 Direct Catalytic Asymmetric Aldol Reaction with a-Hydroxy Ketones.2.4 Direct Catalytic Asymmetric Mannich-Type Reactions.2.5 Direct Catalytic Asymmetric Michael Reaction.2.6 Nitroaldol (Henry) Reaction.2.7 Conclusions.References.3 Group 13-Alkali Metal Heterobimetallic Asymmetric Catalysis (Takashi Ohshima and Masakatsu Shibasaki).3.1 Introduction.3.2 Catalytic Asymmetric Michael Reaction of Stabilized Carbon Nucleophiles.3.2.1 Development of ALB - The First Example of a Group 13-Alkali Metal Heterobimetallic Asymmetric Catalyst.3.2.2 Development of the Second-Generation Heterobimetallic Catalysts -Self-Assembly of Heterobimetallic Catalysts and Reactive Nucleophiles.3.3 Catalytic Asymmetric Ring-Opening Reaction of meso-Epoxides.3.3.1 Ring-Opening Reaction with Thiols.3.3.2 Ring-Opening Reaction with Phenolic Oxygen - Development of a Novel Linked-BINOL Complex.3.4 Catalytic Asymmetric Mannich Reactions.3.4.1 Direct Catalytic Asymmetric Mannich-Type Reaction of Unmodified Ketones.3.4.2 Enantio- and Diastereoselective Catalytic Nitro-Mannich Reactions.3.5 Catalytic Asymmetric Hydrophosphonylation and Hydrophosphinylation of Aldehydes.3.5.1 Catalytic Asymmetric Hydrophosphonylation.3.5.2 Catalytic Asymmetric Hydrophosphinylation.3.6 Conclusion.References.4 Rare Earth Bimetallic Asymmetric Catalysis (Motomu Kanai and Masakatsu Shibasaki).4.1 Introduction.4.2 Catalytic Asymmetric Cyanosilylation of Ketones.4.2.1 Catalytic Asymmetric Synthesis of a Camptothecin Intermediate: Discovery of an (S)-Selective Lanthanide Bimetallic Catalyst for the Cyanosilylation of Ketones.4.2.2 Generality of Catalytic Asymmetric Cyanosilylation of Ketones Using Lanthanide Bimetallic Complexes.4.2.3 Reaction Mechanism.4.2.4 Application to Catalytic Enantioselective Synthesis of an Oxybutynin Intermediate.4.2.5 Catalytic Enantioselective Cyanosilylation of Ketones Containing Sterically Similar Substituents.4.3 Catalytic Enantioselective Strecker Reaction of Ketoimines.4.4 Catalytic Enantioselective Ring-Opening of meso-Epoxides with TMSCN.4.5 Conclusion.References and Notes.5 Rare Earth-Alkali Metal Heterobimetallic Asymmetric Catalysis (Shigeki Matsunaga and Masakatsu Shibasaki).5.1 Introduction.5.2 Development and Structural Analysis of Rare Earth-Alkali Metal Heterobimetallic Complexes.5.3 Nitroaldol Reaction.5.4 Direct Aldol Reaction with LLB * KOH Complex.5.5 Application to Catalytic Asymmetric 1,4-Addition Reactions.5.6 Other Examples.5.7 Miscellaneous Examples.5.8 Summary.References and Notes.6 Catalytic and Stoichiometric Transformations by Multimetallic Rare Earth Metal Complexes (Zhaomin Hou).6.1 Introduction.6.2 Binuclear Alkynide Complexes Bearing Silylene-Linked Cyclopentadienyl-Amido Ligands6.2.1 Synthesis and Structure.6.2.2 Catalytic Dimerization of Terminal Alkynes.6.2.3 Polymerization of Aromatic Diynes and Block Copolymerization of Aromatic Diynes with Caprolactone.6.3 Binuclear Alkyl and Hydrido Complexes Bearing Silylene-Linked Cyclopentadienyl-Phosphido Ligands.6.3.1 Synthesis and Structure.6.3.2 Catalytic Hydrosilylation of Alkenes.6.3.3 Stereospecific 3,4-Polymerization of Isoprene.6.4 Polynuclear Hydrido Complexes Bearing the C5Me4SiMe3 Ligand.6.4.1 Synthesis and Structure.6.4.2 Hydrogenation of Unsaturated C-C Bonds.6.4.3 Reduction of Nitriles to Imido Species.6.4.4 Reactions with Lactones, Carbon Dioxide, and Isocyanates.6.5 Polynuclear Imido Complexes Bearing the C5Me4SiMe3 Ligand.6.5.1 Nitrile Insertion and Hydrogen Transfer.6.5.2 Catalytic Cyclotrimerization of Benzonitrile.6.6 Outlook.References.7 Bimetallic Transition Metal Catalysts for Organic Oxidation (Patrick M. Henry).7.1 Introduction.7.2 Homobinuclear Systems.7.2.1 CuII and FeIII Catalysts.7.2.2 PdII Catalysis.7.3 Heterogeneous Catalysts.7.4 Homogeneous Catalysis.7.4.1 In the Absence of Other Redox Agents.7.4.2 In the Presence of Other Redox Reagents.7.4.3 CoIII Catalysis.7.4.4 MoVI Catalysis.7.5 Heterobinuclear Systems.7.5.1 PdII Plus Another Metal.7.5.2 FeIII Plus Another Metal.7.5.3 RuII Plus Other Metals.7.5.4 RhIII and Other Metals.References.8 Bimetallic Oxidation Catalysts: Hydrogen Peroxide Generation and Its Use in Hydrocarbon Oxidation (Joseph E. Remias and Ayusman Sen).8.1 Introduction.8.2 Metal-Catalyzed Formation of Hydrogen Peroxide.8.3 Metal-Catalyzed Decomposition of Hydrogen Peroxide.8.4 Bimetallic Hydrogen Peroxide Generation and Hydrocarbon Oxidation.8.5 Conclusion.References.9 Two Approaches to Multimetallic Catalysis: Combined Use of Metal Complexes and Multinuclear Complex Catalysts (Youichi Ishii and Masanobu Hidai).9.1 Introduction.9.2 Combined Use of Metal Complexes.9.2.1 Homologation and Hydroformylation by Co-Ru Catalysts.9.2.2 Carbonylation Reactions of Aryl Iodides by Pd-Ru and Pd-Co Systems.9.2.3 Selective Hydroformylation of Internal Alkynes by Pd-Co Catalysts.9.3 Multimetallic Complex Catalysts.9.3.1 Reactions Catalyzed by Thiolato-Bridged Dinuclear Ruthenium Complexes.9.3.2 Catalytic Transformations of Alkynes by Tri- and Tetranuclear Sulfido Clusters.9.4 Concluding Remarks.References.10 Dirhodium Tetraphosphine Catalysts (George G. Stanley).10.1 Dirhodium Tetraphosphine Hydroformylation Catalyst.10.2 In Situ Spectroscopic Studies - Fragmentation Problems.10.3 Effect of Water on Hydroformylation.10.4 Unusual Inhibitory Effect of PPh3.10.5 Catalyst Binding Site Considerations.10.6 Future Directions.References.11 Catalysis by Homo- and Heteronuclear Polymetallic Systems (I. I. Moiseev, A. E. Gekhman, M. V. Tsodikov, V. Ya. Kugel, F. A. Yandieva, L. S. Glebov, G. Yu. Kliger, A. I. Mikaya, V. G. Zaikin, Yu. V. Maksimov, D. I. Kochubey, V. V. Kriventsov, V. P. Mordovin, and J. A. Navio).11.1 Introduction.11.2 Palladium Giant Cluster Catalysis.11.3 TiFe0.95Zr0.03Mo0.02 Intermetallic and Its Hydrides.11.3.1 Capacity of the Intermetallic for the Absorption and Thermal Desorption of H2.11.3.2 Structure of Intermetallic Hydrides and Strongly Bound Hydrogen.11.4 Stoichiometric CO2 Reduction.11.4.1 Reduction of CO2 with Hydrocarbons.11.4.2 Mechanistic Aspects: Role of SBH in Selective CO2 Reduction.11.5 Reductive Dehydration of Alcohols.11.5.1 Cycloalkanones and Cycloalkanols.11.5.2 Benzyl Alcohol and Benzaldehyde.11.5.3 3-Methylbutan-1-ol.11.5.4 2-Methylpropan-1-ol.11.5.5 Ethanol.11.5.6 Mechanistic Speculations.11.6 Conclusion.References.Subject Index.

Author Biography:
Born in 1947, Masakatsu Shibasaki gained his PhD from the University of Tokyo in 1974. Since 1991 he is professor at the University of Tokyo. Masakatsu Shibasaki has received many awards such as the Fluka Prize (Reagent of the Year), the Elsevier Award for Inventiveness in Organic Chemistry, the Pharmaceutical Society of Japan Award, the ACS Award (Arthur C. Cope Senior Scholar Award), and the National Prize of Purple Ribbon. Professor Shibasaki's research interests include asymmetric catalysis, including asymmetric Heck reactions and reactions promoted by asymmetric bifunctional complexes, as well as the medicinal chemistry of biologically significant compounds. Yoshinori Yamamoto was born in Kobe, Japan, and received his M.S. and Ph.D. degrees from Osaka University. In 1986 he moved to Tohoku University to take up his present position, Professor of Chemistry. He was awarded the Chemical Society of Japan Award for Young Chemists (1976), the Chemical Society of Japan Award (1996), and the Humboldt Research Award (2002). He is the Regional Editor of Tetrahedron Letters and Volume Editor of Science of Synthesis, and