Multimetallic Catalysts in Organic Synthesis

Advances in catalytic asymmetric and non–asymmetric syntheses with transition metal catalysts are reaching a plateau, while certain fields among them have already matured. This book promotes the prospect of a breakthrough in the intelligent use of multimetallic catalysts.
The 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. The combination of different metals to create one selective and active catalyst is all set to open the door for many new reactions.
In ten chapters, the international team of expert authors treats asymmetric syntheses, new transformations, and organometallic reactions using homo– and hetero–multimetallic catalysts. Written mainly for advanced researchers, this very timely publication is of significant benefit to organic and organometallic chemists in both academia and industry.

Spis treści:
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 π–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 ð–All ylpalladium 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 á–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 Reacti ve 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 Ligands
6.2.1 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