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電子書籍詳細


洋書 kinoppy

有機合成におけるコバルト触媒:手法と反応

Cobalt Catalysis in Organic Synthesis : Methods and Reactions

1

Hapke, Marko (EDT)   Hilt, Gerhard (EDT)

Wiley-VCH 2019/12
480p.
出版国: DE
ISBN: 9783527344505
eISBN: 9783527814862
KNPID: EY00372054
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Full Description

Provides a much-needed account of the formidable "cobalt rush" in organic synthesis and catalysis

Over the past few decades, cobalt has turned into one of the most promising metals for use in catalytic reactions, with important applications in the efficient and selective synthesis of natural products, pharmaceuticals, and new materials.
Cobalt Catalysis in Organic Synthesis: Methods and Reactions provides a unique overview of cobalt-catalysed and -mediated reactions applied in modern organic synthesis. It covers a broad range of homogeneous reactions, like cobalt-catalysed hydrogenation, hydrofunctionalization, cycloaddition reactions, C-H functionalization, as well as radical and biomimetic reactions.
  • First comprehensive book on this rapidly evolving research area
  • Covers a broad range of homogeneous reactions, such as C-H activation, cross-coupling, synthesis of heterocyclic compounds (Pauson-Khand), and more
  • Chapters on low-valent cobalt complexes as catalysts in coupling reactions, and enantioselective cobalt-catalyzed transformations are also included
  • Can be used as a supplementary reader in courses of advanced organic synthesis and organometallic chemistry
Cobalt Catalysis in Organic Synthesis is an ideal book for graduates and researchers in academia and industry working in the field of synthetic organic chemistry, catalysis, organometallic chemistry, and natural product synthesis.

Table of Contents

Preface xiii

1 Introduction to Cobalt Chemistry and Catalysis 1
Marko Hapke and Gerhard Hilt

1.1 Introduction 1

1.2 Organometallic Cobalt Chemistry, Reactions, and Connections to Catalysis 4

1.2.1 Cobalt Compounds and Complexes of Oxidation States +3 to −1 4

1.2.1.1 Co(III) Compounds 5

1.2.1.2 Co(II) Compounds 5

1.2.1.3 Co(I) Compounds 7

1.2.1.4 Co(0) Compounds 8

1.2.1.5 Co(−I) Compounds 9

1.2.2 Bioorganometallic Cobalt Compounds 10

1.3 Applications in Organic Synthesis and Catalytic Transformations 12

1.4 Conclusion and Outlook 19

Abbreviations 20

References 20

2 Homogeneous Cobalt-Catalysed Hydrogenation Reactions 25
Kathrin Junge and Matthias Beller

2.1 Introduction 25

2.2 Hydrogenation of C—C Multiple Bonds (Alkenes, Alkynes) 25

2.3 Hydrogenation of Carbonyl Compounds (Ketones, Aldehydes, Carboxylic Acid Derivatives, CO2) 34

2.3.1 Ketones and Aldehydes 34

2.3.2 Carboxylic Acid Derivatives (Acids, Esters, Imides) 39

2.3.3 Hydrogenation of Carbon Dioxide 47

2.4 Hydrogenation of CX Multiple Bonds (Imines, Nitriles) 52

2.4.1 Nitrile Hydrogenation 52

2.4.2 Imine Hydrogenation 55

2.4.3 Hydrogenation of N-Heterocycles 56

2.5 Summary and Conclusions 58

2.6 Selected Experimental Procedures 59

2.6.1 Synthesis of Cobalt Complex [(PNHPCy)Co(CH2SiMe3)]BArF4 (8a) 59

Abbreviations 60

References 61

3 Synthesis of C—C Bonds by Cobalt-Catalysed Hydrofunctionalisations 67
Daniel K. Kimand Vy M. Dong

3.1 Introduction 67

3.2 Cobalt-Catalysed C—C Bond Formations via Hydrofunctionalisation 67

3.2.1 Hydroformylation 67

3.2.2 Hydroacylation 68

3.2.3 Hydrovinylation 74

3.2.4 Hydroalkylation 78

3.2.5 Hydrocyanation 80

3.2.6 Hydrocarboxylation 81

3.3 Summary and Conclusions 83

Abbreviations 84

References 85

4 Cobalt-Catalysed C–H Functionalisation 89
Naohiko Yoshikai

4.1 Introduction 89

4.2 Low-valent Cobalt Catalysis 91

4.2.1 C–H Functionalisation with In Situ-Reduced Cobalt Catalysts 91

4.2.1.1 Hydroarylation of Alkynes and Alkenes 91

4.2.1.2 C–H Functionalisation with Electrophiles 98

4.2.1.3 C–H Functionalisation with Organometallic Reagents 103

4.2.1.4 C–H Functionalisation via 1,4-Cobalt Migration 103

4.2.1.5 Hydroacylation 103

4.2.2 C–H Functionalisation with Pincer-Type Ligands and Related Well-Defined Cobalt Catalysts 105

4.3 High-valent Cobalt Catalysis 106

4.3.1 Chelation-Assisted C–H Functionalisation with Cp*CoIII Catalysts 106

4.3.1.1 C—H Addition to Polar C=X Bonds 108

4.3.1.2 Reaction with Alkynes, Alkenes, and Allenes 111

4.3.1.3 Reaction with Formal Nitrene or Carbene Precursors 121

4.3.1.4 Reaction with E–X-type Electrophiles 126

4.3.1.5 Miscellaneous 128

4.3.2 Bidentate Chelation-Assisted C–H Functionalisation with CoIII Catalysts 130

4.3.2.1 Reaction with Alkynes, Alkenes, and Allenes 131

4.3.2.2 Dehydrogenative Cross-coupling Reactions 139

4.3.2.3 Carbonylation and Related Transformations 143

4.3.2.4 Miscellaneous Transformations 144

4.3.3 Miscellaneous 146

4.4 Summary and Outlook 146

Abbreviations 150

References 151

5 Low-valent Cobalt Complexes in C–X Coupling and Related Reactions 163
Céline Dorval and Corinne Gosmini

5.1 Introduction 163

5.2 Cobalt-Catalysed Coupling Reactions with Stoichiometric Organometallic Reagents 163

5.2.1 Cobalt-Catalysed Coupling Reactions with Grignard Reagents 163

5.2.1.1 Csp2— CspBond Formation 164

5.2.1.2 Csp2— CspBond Formation 168

5.2.1.3 Csp— CspBond Formation 173

5.2.1.4 Csp— CspBond Formation 173

5.2.1.5 Csp3— CspBond Formation 175

5.2.2 Cobalt-Catalysed Coupling Reactions with Organozinc Reagents 179

5.2.2.1 Csp— Csp2/Csp— CspBond Formation 179

5.2.2.2 Csp2— CspBond Formation 181

5.2.2.3 Csp2— CspBond Formation 183

5.2.2.4 Csp2—CN Bond Formation 186

5.2.2.5 Csp2—CO Bond Formation 186

5.2.3 Carbon–Heteroatom Bond Formation 187

5.2.3.1 C—N Bond Formation 187

5.2.3.2 C—B Bond Formation 188

5.2.4 Cobalt-Catalysed Coupling Reactions with Organoboron Reagents 188

5.3 Cobalt-Catalysed Coupling Reactions with Organomanganese Reagents 192

5.4 Cobalt-Catalysed Coupling Reactions with Copper Reagents 192

5.5 Cobalt-Catalysed Reductive Cross-coupling Reactions 193

5.5.1 Csp2—Csp2 Bond Formation 193

5.5.2 Csp2—Csp2 Bond Formation 196

5.5.3 Couplings with Benzylic Compounds 196

5.5.4 Couplings with Allylic Acetates 197

5.5.5 Csp3—Csp3 Carbon Bond Forming Reactions 197

5.6 Overview and Perspectives 199

5.7 Abbreviations 200

References 201

6 Ionic and Radical Reactions of 𝛑-Bonded Cobalt Complexes 207
Gagik G.Melikyan and Elen Artashyan

6.1 Introduction 207

6.2 Cobalt-Alkyne Complexes: Electrophilic Reactions 209

6.2.1 Intramolecular Diels–Alder Reactions 210

6.2.2 Assembling Tricyclic Ring Systems 211

6.2.3 Assembling Bicyclic Ring Systems: Decalines 212

6.2.4 Assembling Heterocyclic Ring Systems: Benzopyrans 212

6.2.5 Synthesis of Enediynes 213

6.2.6 Assembling Strained Ring Systems 213

6.2.7 Assembling Natural Carbon Skeletons 215

6.3 CobaltAlkyne Complexes: Radical Reactions 217

6.4 Cobalt-1,3-enyne Complexes: Electrophilic Reactions 226

6.5 Cobalt-1,3-enyne Complexes: Radical Reactions 228

6.6 Prospects 228

Abbreviations 230

References 230

7 Cobalt-Catalysed Cycloaddition Reactions 235
Gerhard Hilt

7.1 Introduction 235

7.2 Four-Membered Carbocyclic Ring Formation Reactions 235

7.2.1 [2+2] Cycloaddition of Two Alkenes 235

7.2.2 [2+2] Cycloaddition of an Alkene and an Alkyne 237

7.2.3 [2+2] Cycloaddition of Two Alkynes 238

7.3 Six-Membered Ring Formation Reactions 240

7.3.1 Cobalt-Catalysed Diels–Alder Reactions 240

7.3.2 Cobalt-Catalysed [2+2+2] Cycloaddition Reactions Other than Cyclotrimerisation of Alkynes 248

7.3.3 Cobalt-Catalysed Benzannulation Reactions 249

7.4 Synthesis of Larger Carbocyclic Ring Systems 250

7.4.1 [3+2+2] and [5+2] Cycloaddition Reaction 250

7.4.2 [6+2] Cycloaddition Reaction 251

7.5 Conclusions 253

Abbreviations 255

References 255

8 Recent Advances in the Pauson–Khand Reaction 259
David M. Lindsay and William J. Kerr

8.1 Introduction 259

8.2 Advances in the PausonKhand Reaction 259

8.2.1 New Methods to Promote the PausonKhand Reaction 259

8.2.1.1 Flow Chemistry Applications of the PausonKhand Reaction 260

8.2.1.2 New Promoters 261

8.2.2 Novel Substrates 264

8.2.2.1 Maleimides as Alkene Partners 264

8.2.2.2 Novel Enyne Substrates 265

8.2.2.3 Strained Reaction Partners 268

8.3 Asymmetric PausonKhand Reaction 269

8.4 Mechanistic and Theoretical Studies 273

8.5 Total Synthesis 276

8.5.1 Synthesis of (+)-Ingenol 276

8.5.2 Towards Retigeranic Acid A 277

8.5.3 The Total Synthesis of Astellatol 278

8.5.4 The Total Synthesis of 2-epi-𝛼-Cedrene-3-one 279

8.6 Summary and Conclusions 280

8.7 Practical Procedures for Stoichiometric and Substoichiometric PausonKhand Reactions 281

Abbreviations 282

References 283

9 Cobalt-Catalysed [2+2+2] Cycloadditions 287
Tim Gläsel and Marko Hapke

9.1 Introduction 287

9.2 Reaction Mechanisms of Cobalt-Catalysed Cyclotrimerisations 288

9.3 Cobalt-Based Catalysts and Catalytic Systems 292

9.4 CpCo-Based Cyclisations 296

9.4.1 Carbocyclic Compounds 296

9.4.2 Heterocyclic Compounds 298

9.5 Non-CpCo-Based Cobalt-Catalysed Cyclisations 302

9.5.1 Co2(CO)8-Mediated Cyclisations of Carbocyclic Compounds 302

9.5.2 In Situ-Generated Catalysts and Precatalysts in Carbocyclisations of Alkynes 304

9.5.3 In Situ-Generated Catalysts in the Cyclisation of Alkynes to Heterocyclic Compounds 309

9.6 Cobalt-Mediated Asymmetric [2+2+2] Cycloadditions 313

9.7 Cobalt-Mediated Cyclisations in Natural Product Synthesis 317

9.8 Novel Developments of Cobalt-Mediated Cycloaddition Catalysis 322

9.9 Summary and Outlook 326

9.10 Selected Experimental Procedures 327

9.10.1 Synthesis of [CpCo(CO)(trans-MeO2CCH=CHCO2Me)] (PCAT5) 327

9.10.2 Synthesis of [CpCo(CO){P(OEt)3}] and [CpCo(trans-MeO2CCH=CHCO2Me){P(OEt)3}] (PCAT8) 327

Abbreviations 328

References 330

10 Enantioselective Cobalt-Catalysed Transformations 337
H. Pellissier

10.1 Introduction 337

10.2 Synthesis of Chiral Acyclic Compounds Through Enantioselective Cobalt-Catalysed Reactions 338

10.2.1 Michael and (Nitro)-Aldol Reactions 338

10.2.1.1 Michael Reactions 338

10.2.1.2 (Nitro)-Aldol Reactions 342

10.2.2 Reduction Reactions 346

10.2.2.1 Reductions of Carbonyl Compounds and Derivatives 346

10.2.2.2 Reductions of Alkenes 349

10.2.3 Ring-Opening Reactions 353

10.2.3.1 Hydrolytic Ring-Openings of Epoxides 353

10.2.3.2 Ring-Openings of Epoxides by Nucleophiles Other than Water 356

10.2.4 Hydrovinylation and Hydroboration Reactions 358

10.2.4.1 Hydrovinylations 358

10.2.4.2 Hydroborations 361

10.2.5 Cross-coupling Reactions 363

10.2.6 Miscellaneous Reactions 366

10.3 Enantioselective Cobalt-Catalysed Cyclisation Reactions 370

10.3.1 [2+1] Cycloadditions 370

10.3.2 Miscellaneous Cycloadditions 379

10.3.2.1 (Hetero)-Diels–Alder Cycloadditions 379

10.3.2.2 1,3-Dipolar Cycloadditions 380

10.3.2.3 Other Cycloadditions 383

10.3.3 Cyclisations Through Domino Reactions 386

10.3.4 Miscellaneous Cyclisations 390

10.4 Conclusions 395

Abbreviations 396

References 397

11 Cobalt Radical Chemistry in Synthesis and Biomimetic Reactions (Including Vitamin B12) 417
Michał Ociepa and Dorota Gryko

11.1 Introduction 417

11.2 Cobalt-Mediated Reactions of Carbon-Centred Radicals 417

11.2.1 Homocoupling Reactions 418

11.2.2 Cross-coupling Reactions 420

11.2.3 Additions to Alkenes and Alkynes 423

11.2.4 Cyclisation Reactions 425

11.2.5 Dehalogenation 429

11.2.6 Oxidation 431

11.2.7 Acylation 433

11.2.8 Applications of Cobalt Complexes in Photoredox Catalysis 435

11.2.9 Miscellaneous Reactions 438

11.3 Cobalt-Mediated Reactions of Heteroatom-Centred Radicals 440

11.3.1 Nitrogen-Centred Radicals 440

11.3.2 Other Types of Radicals 441

11.4 Overview and Conclusion 442

11.5 Experimental Section 443

11.5.1 Synthesis of Chloro(pyridine)cobaloxime Co(dmgH)2Cl(py) (116) 443

11.5.2 Synthesis of Aqua(cyano)heptamethyl Cobyrinate (56b) – Hydrophobic Vitamin B12 Model 444

11.5.3 General Procedure for Synthesis of Co(II)(salen) and Co(III)(salen) Complexes 445

Abbreviations 445

References 446

Index 453