Cleavage of Carbon-carbon Single Bonds by

Edited by leading experts and pioneers in the field, this is the first up-to-date book on this hot topic.
The authors provide synthetic chemists with different methods to activate carbon-carbon sigma bonds in organic molecules promoted by transition metal complexes. They explain the basic principles and strategies for carbon-carbon bond cleavage and highlight recently developed synthetic protocols based on this methodology. In so doing, they cover cleavage of C-C bonds in strained molecules, reactions involving elimination of carbon dioxide and ketones, reactions via retroallylation, and cleavage of C-C bonds of ketones and nitriles.
The result is an excellent information source for researchers in academia and industry working in the field of synthetic organic chemistry, while equally serving as supplementary reading for advanced courses in organometallic chemistry and catalysis.

Masahiro Murakami is Professor of Organometallic Chemistry at Kyoto University, Japan. He received his D.Sc. from the University of Tokyo, Japan, under the supervision of Prof. T. Mukaiyama in 1984. He held an assistant position at the same university (1984-1987, with Prof. T. Mukaiyama) and at Kyoto University (1987-1993, with Prof. Y. Ito). From 1991 to 1992, he worked for Prof. A. Eschenmoser at ETH Zürich, Switzerland, as a postdoctoral fellow. He was promoted to Associate Professor in 1993 and Professor in 2002 at Kyoto University. He is a recipient of the Chemical Society of Japan Award for Creative Work (2004) and the Nagoya Silver Medal (2008), Synthetic Organic Chemistry Award, Japan (2013), and Humboldt Research Award (2013). His research interests are directed toward the development of new reactions, including transition-metal-catalyzed reactions involving carbon-carbon bond formation or cleavage, electrocyclic reactions, and synthesis of heterocycles.

Naoto Chatani is Professor of Molecular Design Chemistry at Osaka University, Japan. He studied chemistry at Osaka University, Japan, and received his Ph.D. in 1984 under the guidance of Profs. N. Sonoda and S. Murai. In 1984 he joined the Institute of Scientific and Industrial Research at Osaka University and worked in the laboratory of Prof. T. Hanafusa. After postdoctoral studies with Prof. S. E. Denmark at the University of Illinois (Urbana-Champaign, USA, 1988-1989), he moved back to Osaka University and worked with Prof. S. Murai as Assistant Professor. He was promoted to Associcate Professor in 1992 and Professor in 2003. He received the Young Chemist Award of the Chemical Society of Japan (1991) and the fourth Green and Sustainable Chemistry Award by the Minister of Education, Sports, Culture, Science and Technology (2005). His current research interests center on the area of catalysis.

Preface IX

List of Contributors XI

1 Fundamental Reactions to Cleave Carbon–Carbon σ-Bonds with Transition Metal Complexes 1
Masahiro Murakami and Naoki Ishida

1.1 Introduction 1

1.2 Oxidative Addition 1

1.2.1 Oxidative Addition Utilizing Ring Strain 3

1.2.2 Chelation-Assisted Oxidative Addition 5

1.2.3 Oxidative Addition Driven by Aromatization 6

1.2.4 Oxidative Addition of Ketones 7

1.2.5 Oxidative Addition of Nitriles 11

1.2.6 Others 13

1.3 β-Carbon Elimination 14

1.3.1 β-Carbon Elimination of Late Transition Metal Alkyls 15

1.3.2 β-Carbon Elimination from Early Transition Metal Alkyls 16

1.3.3 β-Carbon Elimination of Late Transition Metal Alcoholates 17

1.4 Retroallylation 20

1.5 Migratory Deinsertion of a Carbonyl Group 22

1.6 Decarboxylation 24

1.7 Retro-oxidative Cyclization 25

1.8 1,2-Migration 27

1.9 Cleavage of C–C Multiple Bonds 29

1.10 Summary 30

References 30

2 Reactions of Three-Membered Ring Compounds 35
Takanori Matsuda

2.1 Introduction 35

2.2 Cyclopropanes 35

2.3 Bicyclo[1.1.0]butanes 40

2.4 Bicyclo[2.1.0]pentanes 43

2.5 Quadricyclanes and Related Compounds 45

2.6 Spiropentanes 47

2.7 Cyclopropanols 48

2.8 Vinylcyclopropanes 51

2.9 Methylenecyclopropanes 59

2.10 Alkynylcyclopropanes 70

2.11 Cyclopropyl Ketones and Imines 71

2.12 Cyclopropenes 73

2.13 Benzocyclopropenes 78

2.14 Cyclopropenones 80

2.15 Conclusion 82

References 83

3 Reactions of Four-Membered Ring Compounds 89
Takanori Matsuda

3.1 Introduction 89

3.2 Cubane Derivatives 89

3.3 Biphenylenes 90

3.4 Vinylcyclobutane and Methylenecyclobutane Derivatives 93

3.5 Cyclobutanol and Cyclobutanone Derivatives 95

3.5.1 Reactions Involving β-Carbon Elimination of Transition Metal Cyclobutanolates 95

3.5.2 Reactions Involving Formation of Five-Membered Metallacycles 108

3.6 Cyclobutenones and Cyclobutenediones 112

3.7 Conclusion 115

References 115

4 Reactions Involving Elimination of CO2 and Ketones 119
Tetsuya Satoh and Masahiro Miura

4.1 Introduction 119

4.2 Reactions of Benzoic Acids 119

4.2.1 Arylation 119

4.2.2 Alkenylation 127

4.2.3 Annulation 130

4.2.4 Miscellaneous Reactions 132

4.3 Reactions of Heteroarenecarboxylic Acids 134

4.4 Reactions of Acrylic Acids 139

4.5 Reactions of Propiolic Acids 142

4.6 Reactions of α-Keto Carboxylic Acids 144

4.7 Reactions of Alkanoic Acids 148

4.8 Reactions of Tertiary Alcohols 151

4.8.1 Arylation 151

4.8.2 Alkenylation, Annulation, and Alkylation 155

4.9 Summary and Conclusions 159

References 160

5 Retro-allylation and Deallylation 165
Hideki Yorimitsu

5.1 Introduction 165

5.2 Retro-allylation 165

5.2.1 Ruthenium Catalysis: The Pioneer 167

5.2.2 Palladium Catalysis: Regio- and Stereoselective Allylation of Aryl Halides 168

5.2.2.1 Advantage of Palladium-Catalyzed Allylation via Retro-allylation 168

5.2.2.2 Palladium-Catalyzed Regio- and Stereoselective Allylation via Retro-allylation 170

5.2.2.3 Variants of Palladium-Catalyzed Retro-allylation 176

5.2.3 Nickel Catalysis 179

5.2.4 Rhodium Catalysis 181

5.2.5 Copper Catalysis 184

5.3 Deallylation 185

5.3.1 Oxidative Addition of Allylic Compounds 185

5.3.2 Metalation–β-Carbon Elimination Sequence 187

5.4 Summary and Conclusions 189

References 190

6 Reactions via Cleavage of Carbon–Carbon Bonds of Ketones and Nitriles 193
Mamoru Tobisu

6.1 Introduction 193

6.2 Catalytic Reactions of Ketones via C–C Bond Cleavage 194

6.2.1 Reactions of Ketones without Chelation Assistance 194

6.2.2 Reactions of Ketones Containing a Directing Group 196

6.2.3 Reactions of Ketones Using a Temporary Directing Group 200

6.2.4 C–C Bond Cleavage of Ketones via Pathways Other than Oxidative Addition 202

6.2.4.1 C–C Bond Cleavage of 1,3-Dicarbonyl Compounds 202

6.2.4.2 C–C Bond Cleavage of Ketones Other than 1,3-Dicarbonyl Compounds 203

6.3 Catalytic Reactions of Nitriles via C–C Bond Cleavage 205

6.3.1 C–CN Bond Cleavage via Oxidative Addition 205

6.3.2 C–CN Bond Cleavage via Silylmetalation/Isocyanide Extrusion Sequence 212

6.3.3 C–CN Bond Cleavage via Other Mechanisms 215

6.4 Summary and Outlook 216

References 217

7 Miscellaneous 221
Masahiro Murakami and Naoki Ishida

7.1 Introduction 221

7.2 Cleavage of C–C Single Bonds 221

7.3 Cleavage of C=C Double Bonds 235

7.4 Cleavage of C–C Bonds of Aromatics 237

7.5 Cleavage of C≡C Triple Bonds 242

7.6 Summary 248

References 248

8 Total Syntheses of Natural Products and Biologically Active Compounds by Transition-Metal-Catalyzed C–C Cleavage 253
Masahiro Murakami and Naoki Ishida

8.1 Introduction 253

8.2 Synthesis of (±)-Nanaomycin A through Alkyne Insertion into a C–C Bond of Benzocyclobutenedione 253

8.3 Enantioselective Synthesis of (−)-Pseudolaric Acid B via an Intramolecular [5+2] Cycloaddition Reaction of a Vinylcyclopropane with an Alkyne 254

8.4 Enantioselective Synthesis of (−)-Esermethole via Asymmetric Alkene Insertion into a C–C Bond of Aryl Cyanides 256

8.5 Enantioselective Synthesis of Benzobicyclo[2.2.2]octenones via Asymmetric Alkene Insertion into a C–C Bond of Cyclobutanones 257

8.6 Synthesis of the Proposed Structure of Cycloinumakiol through Site-Selective Insertion of Alkenes into a C–C Bond of Benzocyclobutenones 259

8.7 Enantioselective Synthesis of (−)-(R)-Herbertenol through Asymmetric C–C Cleavage 260

8.8 Enantioselective Synthesis of (+)-Laurene via Ring-Expansion of 1-Vinylcyclobutanol 261

8.9 Synthesis of (±)-Cuparenone through Skeletal Reorganization of Spiropentanes 262

8.10 Total Synthesis of (−)-Cyanthiwigin F by Decarboxylative Asymmetric Allylation 264

8.11 Total Syntheses via Hydrogenolysis of Cyclopropanes 265

8.12 Total Syntheses via Decarbonylation 266

8.13 Summary and Conclusions 269

References 270

Index 273

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Cleavage of Carbon-carbon Single Bonds by Transition Metals

Summary

Author Biography

Table of Contents

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