Multimetallic Catalysts in Organic Synthesis

, by Shibasaki, Masakatsu; Yamamoto, Yoshinori

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ISBN: 9783527308286 | 3527308288
Cover: Hardcover
Copyright: 10/15/2004

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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.

Preface

List of Contributors

xiii

1 Organic Synthesis with Bimetallic Systems

(52)

Shin Kamijo and Yoshinori Yamamoto

1.1 Introduction

(2)

1.2 Reactions Promoted by a Combination of Catalytic and Stoichiometric Amounts of Metals

(19)

1.2.1 Transition Metal-Catalyzed Cross-Coupling Reactions

(4)

1.2.2 The Wacker Reaction

(3)

1.2.3 The Heck Reaction

(2)

1.2.4 Reactions Involving it-Allylpalladium Intermediates

(6)

1.2.4.1 Electrophilic Reactions

(1)

1.2.4.2 Nucleophilic Reactions

(5)

1.2.5 Nickel-Catalyzed Three-Component Coupling Reaction

(2)

1.2.6 The Nozaki-Hiyama-Kishi Reaction

(2)

1.3 Reactions Promoted by a Combination of Catalytic Amounts of Two Metals

(26)

1.3.1 Transition Metal Catalyzed Cross-Coupling Reactions

(5)

1.3.1.1 The Stille Reaction

(1)

1.3.1.2 The Hiyama Reaction

(1)

1.3.1.3 The Sonogashira Reaction

(3)

1.3.2 The Wacker Reaction

(2)

1.3.3 Reactions Involving mt-Allylpalladium Intermediates

(1)

1.3.4 Transition Metal Catalyzed Cyclization Reactions

(9)

1.3.4.1 [3+2] Cycloaddition Reactions

(2)

1.3.4.2 Intramolecular [n+2] Cyclization Reactions

(3)

1.3.4.3 Intermolecular [n+2+2] Cyclotrimerization Reactions

(1)

1.3.4.4 [2+2+1] Cycloaddition Reactions; The Pauson-Khand Reaction

(1)

1.3.4.5 Cycloisomerization Reactions

(1)

1.3.4.6 Indole-Forming Reaction

(1)

1.3.4.7 Furan- and Pyrrole-Forming Reactions

(1)

1.3.5 Reactions Involving Nucleophilic Addition of Carbonyl Compounds

(3)

1.3.5.1 The Aldol Reaction

(1)

1.3.5.2 Alkynylation Reactions

(1)

1.3.5.3 Conjugate Addition Reactions

(1)

1.3.6 Miscellaneous Reactions

(15)

1.3.6.1 Transition Metal Catalyzed Reactions

(2)

1.3.6.2 Lewis Acid Catalyzed Reactions

(2)

1.3.6.3 Sequential Reactions

(2)

References

(5)

2 Zinc Polymetallic Asymmetric Catalysis

(24)

Naoya Kumagai and Masakatsu Shibasaki

2.1 Introduction

(1)

2.2 Asymmetric Alternating Copolymerization with Dimeric Zn Complexes

(4)

2.3 Direct Catalytic Asymmetric Aldol Reaction with Zn Polymetallic Catalysts

(9)

2.3.1 Introduction

(1)

2.3.2 Direct Catalytic Asymmetric Aldol Reaction with Methyl Ketones

(2)

2.3.3 Direct Catalytic Asymmetric Aldol Reaction with a-Hydroxy Ketones

(6)

2.4 Direct Catalytic Asymmetric Mannich-Type Reactions

(3)

2.5 Direct Catalytic Asymmetric Michael Reaction

(4)

2.6 Nitroaldol (Henry) Reaction

(2)

2.7 Conclusions

(1)

References

(2)

3 Group 13-Alkali Metal Heterobimetallic Asymmetric Catalysis

(26)

Takashi Ohshima and Masakatsu Shibasaki

3.1 Introduction

(1)

3.2 Catalytic Asymmetric Michael Reaction of Stabilized Carbon Nucleophiles

(12)

3.2.1 Development of ALB - The First Example of a Group 13-Alkali Metal Heterobimetallic Asymmetric Catalyst

(5)

3.2.2 Development of the Second-Generation Heterobimetallic Catalysts - Self-Assembly of Heterobimetallic Catalysts and Reactive Nucleophiles

(7)

3.3 Catalytic Asymmetric Ring-Opening Reaction of meso-Epoxides

(6)

3.3.1 Ring-Opening Reaction with Thiols

(3)

3.3.2 Ring-Opening Reaction with Phenolic Oxygen - Development of a Novel Linked-BINOL Complex

(3)

3.4 Catalytic Asymmetric Mannich Reactions

(2)

3.4.1 Direct Catalytic Asymmetric Mannich-Type Reaction of Unmodified Ketones

(1)

3.4.2 Enantio- and Diastereoselective Catalytic Nitro-Mannich Reactions

(1)

3.5 Catalytic Asymmetric Hydrophosphonylation and Hydrophosphinylation of Aldehydes

(2)

3.5.1 Catalytic Asymmetric Hydrophosphonylation

(1)

3.5.2 Catalytic Asymmetric Hydrophosphinylation

(2)

3.6 Conclusion

100

(1)

References

101

(2)

4 Rare Earth Bimetallic Asymmetric Catalysis

103

(18)

Motomu Kanai and Masakatsu Shibasaki

4.1 Introduction

103

(1)

4.2 Catalytic Asymmetric Cyanosilylation of Ketones

104

(9)

4.2.1 Catalytic Asymmetric Synthesis of a Camptothecin Intermediate: Discovery of an (S)-Selective Lanthanide Bimetallic Catalyst for the Cyanosilylation of Ketones

104

(2)

4.2.2 Generality of Catalytic Asymmetric Cyanosilylation of Ketones Using Lanthanide Bimetallic Complexes

106

(2)

4.2.3 Reaction Mechanism

108

(2)

4.2.4 Application to Catalytic Enantioselective Synthesis of an Oxybutynin Intermediate

110

(1)

4.2.5 Catalytic Enantioselective Cyanosilylation of Ketones Containing Sterically Similar Substituents

110

(3)

4.3 Catalytic Enantioselective Strecker Reaction of Ketoimines

113

(2)

4.4 Catalytic Enantioselective Ring-Opening of meso-Epoxides with TMSCN

115

(3)

4.5 Conclusion

118

(1)

References and Notes

118

(3)

5 Rare Earth-Alkali Metal Heterobimetallic Asymmetric Catalysis

121

(22)

Shigeki Matsunaga and Masakatsu Shibasaki

5.1 Introduction

121

(1)

5.2 Development and Structural Analysis of Rare Earth-Alkali Metal Heterobimetallic Complexes

122

(2)

5.3 Nitroaldol Reaction

124

(5)

5.4 Direct Aldol Reaction with LLB • KOH Complex

129

(4)

5.5 Application to Catalytic Asymmetric 1,4-Addition Reactions

133

(5)

5.6 Other Examples

138

(1)

5.7 Miscellaneous Examples

139

(1)

5.8 Summary

140

(1)

References and Notes

141

(2)

6 Catalytic and Stoichiometric Transformations by Multimetallic Rare Earth Metal Complexes

143

(20)

Zhaomin Hou

6.1 Introduction

143

(1)

6.2 Binuclear Alkynide Complexes Bearing Silylene-Linked Cyclopentadienyl-Amido Ligands

144

(4)

6.2.1 Synthesis and Structure

144

(1)

6.2.2 Catalytic Dimerization of Terminal Alkynes

144

(3)

6.2.3 Polymerization of Aromatic Diynes and Block Copolymerization of Aromatic Diynes with Caprolactone

147

(1)

6.3 Binuclear Alkyl and Hydrido Complexes Bearing Silylene-Linked Cyclopentadienyl-Phosphido Ligands

148

(4)

6.3.1 Synthesis and Structure

148

(2)

6.3.2 Catalytic Hydrosilylation of Alkenes

150

(1)

6.3.3 Stereospecific 3,4-Polymerization of Isoprene

151

(1)

6.4 Polynuclear Hydrido Complexes Bearing the C5Me4SiMe3 Ligand

152

(5)

6.4.1 Synthesis and Structure

152

(1)

6.4.2 Hydrogenation of Unsaturated C-C Bonds

153

(2)

6.4.3 Reduction of Nitriles to Imido Species

155

(1)

6.4.4 Reactions with Lactones, Carbon Dioxide, and Isocyanates

155

(2)

6.5 Polynuclear Imido Complexes Bearing the C5Me4SiMe3 Ligand

157

(3)

6.5.1 Nitrile Insertion and Hydrogen Transfer

157

(2)

6.5.2 Catalytic Cyclotrimerization of Benzonitrile

159

(1)

6.6 Outlook

160

(1)

References

161

(2)

7 Bimetallic Transition Metal Catalysts for Organic Oxidation

163

(24)

Patrick M. Henry

7.1 Introduction

163

(1)

7.2 Homobinuclear Systems

164

(7)

7.2.1 CuII and FeIII Catalysts

164

(7)

7.2.2 PdII Catalysis

171

(1)

7.3 Heterogeneous Catalysts

171

(5)

7.4 Homogeneous Catalysis

176

(6)

7.4.1 In the Absence of Other Redox Agents

176

(2)

7.4.2 In the Presence of Other Redox Reagents

178

(3)

7.4.3 CoIII Catalysis

181

(1)

7.4.4 MoVI Catalysis

182

(1)

7.5 Heterobinuclear Systems

182

(1)

7.5.1 PdII Plus Another Metal

182

(1)

7.5.2 FeIII Plus Another Metal

183

(1)

7.5.3 RuII Plus Other Metals

183

(1)

7.5.4 RhIII and Other Metals

183

(1)

References

183

(4)

8 Bimetallic Oxidation Catalysts: Hydrogen Peroxide Generation and Its Use in Hydrocarbon Oxidation

187

(14)

Joseph E. Remias and Ayusman Sen

8.1 Introduction

187

(1)

8.2 Metal-Catalyzed Formation of Hydrogen Peroxide

188

(2)

8.3 Metal-Catalyzed Decomposition of Hydrogen Peroxide

190

(1)

8.4 Bimetallic Hydrogen Peroxide Generation and Hydrocarbon Oxidation

191

(6)

8.5 Conclusion

197

(1)

References

198

(3)

9 Two Approaches to Multimetallic Catalysis: Combined Use of Metal Complexes and Multinuclear Complex Catalysts

201

(24)

Youichi Ishii and Masanobu Hidai

9.1 Introduction

201

(1)

9.2 Combined Use of Metal Complexes

202

(11)

9.2.1 Homologation and Hydroformylation by Co-Ru Catalysts

202

(3)

9.2.2 Carbonylation Reactions of Aryl Iodides by Pd-Ru and Pd-Co Systems

205

(5)

9.2.3 Selective Hydroformylation of Internal Alkynes by Pd-Co Catalysts

210

(3)

9.3 Multimetallic Complex Catalysts

213

(8)

9.3.1 Reactions Catalyzed by Thiolato-Bridged Dinuclear Ruthenium Complexes

213

(5)

9.3.2 Catalytic Transformations of Alkynes by Tri- and Tetranuclear Sulfido Clusters

218

(3)

9.4 Concluding Remarks

221

(1)

References

221

(4)

10 Dirhodium Tetraphosphine Catalysts

225

(24)

George G. Stanley

10.1 Dirhodium Tetraphosphine Hydroformylation Catalyst

225

(5)

10.2 In Situ Spectroscopic Studies - Fragmentation Problems

230

(4)

10.3 Effect of Water on Hydroformylation

234

(5)

10.4 Unusual Inhibitory Effect of PPh3

239

(3)

10.5 Catalyst Binding Site Considerations

242

(2)

10.6 Future Directions

244

(3)

References

247

(2)

11 Catalysis by Homo- and Heteronuclear Polymetallic Systems

249

(42)

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

249

(1)

11.2 Palladium Giant Cluster Catalysis

250

(3)

11.3 TiFe0.95Zr0.03Mo0.02 Intermetallic and Its Hydrides

253

(10)

11.3.1 Capacity of the Intermetallic for the Absorption and Thermal Desorption of H2

255

(2)

11.3.2 Stricture of Intermetallic Hydrides and Strongly Bound Hydrogen

257

(6)

11.4 Stoichiometric CO2 Reduction

263

(8)

11.4.1 Reduction of CO2 with Hydrocarbons

268

(1)

11.4.2 Mechanistic Aspects: Role of SBH in Selective CO2 Reduction

269

(2)

11.5 Reductive Dehydration of Alcohols

271

(16)

11.5.1 Cycloalkanones and Cycloalkanols

273

(4)

11.5.2 Benzyl Alcohol and Benzaldehyde

277

(1)

11.5.3 3-Methylbutan-1-ol

278

(3)

11.5.4 2-Methylpropan-1-ol

281

(1)

11.5.5 Ethanol

282

(1)

11.5.6 Mechanistic Speculations

283

(4)

11.6 Conclusion

287

(1)

References

288

(3)

Subject Index

291

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Multimetallic Catalysts in Organic Synthesis

Summary

Author Biography

Table of Contents

Supplemental Materials

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Multimetallic Catalysts in Organic Synthesis

Summary

Author Biography

Table of Contents

Supplemental Materials

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