Cobalt catalysis in organic synthesis methods and reactions

Cover......Page 1
Title Page......Page 5
Copyright......Page 6
Contents......Page 7
Preface......Page 15
 1.1 Introduction......Page 21
  1.2.1 Cobalt Compounds and Complexes of Oxidation States +3 to -1......Page 24
   1.2.1.2 Co(II) Compounds......Page 25
   1.2.1.3 Co(I) Compounds......Page 27
   1.2.1.4 Co(0) Compounds......Page 28
   1.2.1.5 Co(-I) Compounds......Page 29
  1.2.2 Bioorganometallic Cobalt Compounds......Page 30
 1.3 Applications in Organic Synthesis and Catalytic Transformations......Page 32
 1.4 Conclusion and Outlook......Page 39
 References......Page 40
 2.2 Hydrogenation of CC Multiple Bonds (Alkenes, Alkynes)......Page 45
  2.3.1 Ketones and Aldehydes......Page 54
  2.3.2 Carboxylic Acid Derivatives (Acids, Esters, Imides)......Page 59
  2.3.3 Hydrogenation of Carbon Dioxide......Page 67
  2.4.1 Nitrile Hydrogenation......Page 72
  2.4.2 Imine Hydrogenation......Page 75
  2.4.3 Hydrogenation of N‐Heterocycles......Page 76
 2.5 Summary and Conclusions......Page 78
  2.6.1 Synthesis of Cobalt Complex [(PNHPCy)Co(CH2SiMe3)]BArF4 (8a)......Page 79
 Abbreviations......Page 80
 References......Page 81
  3.2.1 Hydroformylation......Page 87
  3.2.2 Hydroacylation......Page 88
  3.2.3 Hydrovinylation......Page 94
  3.2.4 Hydroalkylation......Page 98
  3.2.5 Hydrocyanation......Page 100
  3.2.6 Hydrocarboxylation......Page 101
 3.3 Summary and Conclusions......Page 103
 Abbreviations......Page 104
 References......Page 105
 4.1 Introduction......Page 109
   4.2.1.1 Hydroarylation of Alkynes and Alkenes......Page 111
   4.2.1.2 C-H Functionalisation with Electrophiles......Page 118
   4.2.1.5 Hydroacylation......Page 123
  4.2.2 C-H Functionalisation with Pincer‐Type Ligands and Related Well‐Defined Cobalt Catalysts......Page 125
  4.3.1 Chelation‐Assisted C-H Functionalisation with Cp*CoIII Catalysts......Page 126
   4.3.1.1 CH Addition to Polar CX Bonds......Page 128
   4.3.1.2 Reaction with Alkynes, Alkenes, and Allenes......Page 131
   4.3.1.3 Reaction with Formal Nitrene or Carbene Precursors......Page 141
   4.3.1.4 Reaction with E-X‐type Electrophiles......Page 146
   4.3.1.5 Miscellaneous......Page 148
  4.3.2 Bidentate Chelation‐Assisted C-H Functionalisation with CoIII Catalysts......Page 150
   4.3.2.1 Reaction with Alkynes, Alkenes, and Allenes......Page 151
   4.3.2.2 Dehydrogenative Cross‐coupling Reactions......Page 159
   4.3.2.3 Carbonylation and Related Transformations......Page 163
   4.3.2.4 Miscellaneous Transformations......Page 164
 4.4 Summary and Outlook......Page 166
 Abbreviations......Page 170
 References......Page 171
  5.2.1 Cobalt‐Catalysed Coupling Reactions with Grignard Reagents......Page 183
   5.2.1.1 Csp2Csp2 Bond Formation......Page 184
   5.2.1.2 Csp2Csp3 Bond Formation......Page 188
   5.2.1.4 CspCsp3 Bond Formation......Page 193
   5.2.1.5 Csp3Csp3 Bond Formation......Page 195
   5.2.2.1 CspCsp2/CspCsp3 Bond Formation......Page 199
   5.2.2.2 Csp2Csp2 Bond Formation......Page 201
   5.2.2.3 Csp2Csp3 Bond Formation......Page 203
   5.2.2.5 Csp2CO Bond Formation......Page 206
   5.2.3.1 CN Bond Formation......Page 207
  5.2.4 Cobalt‐Catalysed Coupling Reactions with Organoboron Reagents......Page 208
 5.4 Cobalt‐Catalysed Coupling Reactions with Copper Reagents......Page 212
  5.5.1 Csp2Csp2 Bond Formation......Page 213
  5.5.3 Couplings with Benzylic Compounds......Page 216
  5.5.5 Csp3Csp3 Carbon Bond Forming Reactions......Page 217
 5.6 Overview and Perspectives......Page 219
 5.7 Abbreviations......Page 220
 References......Page 221
 6.1 Introduction......Page 227
 6.2 Cobalt‐Alkyne Complexes: Electrophilic Reactions......Page 229
  6.2.1 Intramolecular Diels-Alder Reactions......Page 230
  6.2.2 Assembling Tricyclic Ring Systems......Page 231
  6.2.4 Assembling Heterocyclic Ring Systems: Benzopyrans......Page 232
  6.2.6 Assembling Strained Ring Systems......Page 233
  6.2.7 Assembling Natural Carbon Skeletons......Page 235
 6.3 Cobalt-Alkyne Complexes: Radical Reactions......Page 237
 6.4 Cobalt‐1,3‐enyne Complexes: Electrophilic Reactions......Page 246
 6.6 Prospects......Page 248
 References......Page 250
  7.2.1 [2+2] Cycloaddition of Two Alkenes......Page 255
  7.2.2 [2+2] Cycloaddition of an Alkene and an Alkyne......Page 257
  7.2.3 [2+2] Cycloaddition of Two Alkynes......Page 258
  7.3.1 Cobalt‐Catalysed Diels-Alder Reactions......Page 260
  7.3.2 Cobalt‐Catalysed [2+2+2] Cycloaddition Reactions Other than Cyclotrimerisation of Alkynes......Page 268
  7.3.3 Cobalt‐Catalysed Benzannulation Reactions......Page 269
  7.4.1 [3+2+2] and [5+2] Cycloaddition Reaction......Page 270
  7.4.2 [6+2] Cycloaddition Reaction......Page 271
 7.5 Conclusions......Page 273
 References......Page 275
  8.2.1 New Methods to Promote the Pauson-Khand Reaction......Page 279
   8.2.1.1 Flow Chemistry Applications of the Pauson-Khand Reaction......Page 280
   8.2.1.2 New Promoters......Page 281
   8.2.2.1 Maleimides as Alkene Partners......Page 284
   8.2.2.2 Novel Enyne Substrates......Page 285
   8.2.2.3 Strained Reaction Partners......Page 288
 8.3 Asymmetric Pauson-Khand Reaction......Page 289
 8.4 Mechanistic and Theoretical Studies......Page 293
  8.5.1 Synthesis of (+)‐Ingenol......Page 296
  8.5.2 Towards Retigeranic Acid A......Page 297
  8.5.3 The Total Synthesis of Astellatol......Page 298
  8.5.4 The Total Synthesis of 2‐epi‐Cedrene‐3‐one......Page 299
 8.6 Summary and Conclusions......Page 300
 8.7 Practical Procedures for Stoichiometric and Substoichiometric Pauson-Khand Reactions......Page 301
 Abbreviations......Page 302
 References......Page 303
 9.1 Introduction......Page 307
 9.2 Reaction Mechanisms of Cobalt‐Catalysed Cyclotrimerisations......Page 308
 9.3 Cobalt‐Based Catalysts and Catalytic Systems......Page 312
  9.4.1 Carbocyclic Compounds......Page 316
  9.4.2 Heterocyclic Compounds......Page 318
  9.5.1 Co2(CO)8‐Mediated Cyclisations of Carbocyclic Compounds......Page 322
  9.5.2 In Situ‐Generated Catalysts and Precatalysts in Carbocyclisations of Alkynes......Page 324
  9.5.3 In Situ‐Generated Catalysts in the Cyclisation of Alkynes to Heterocyclic Compounds......Page 329
 9.6 Cobalt‐Mediated Asymmetric [2+2+2] Cycloadditions......Page 333
 9.7 Cobalt‐Mediated Cyclisations in Natural Product Synthesis......Page 337
 9.8 Novel Developments of Cobalt‐Mediated Cycloaddition Catalysis......Page 342
 9.9 Summary and Outlook......Page 346
  9.10.2 Synthesis of [CpCo(CO){P(OEt)3}] and [CpCo(trans‐MeO2CCHCHCO2Me){P(OEt)3}] (PCAT8)......Page 347
 Abbreviations......Page 348
 References......Page 350
 10.1 Introduction......Page 357
   10.2.1.1 Michael Reactions......Page 358
   10.2.1.2 (Nitro)‐Aldol Reactions......Page 362
   10.2.2.1 Reductions of Carbonyl Compounds and Derivatives......Page 366
   10.2.2.2 Reductions of Alkenes......Page 369
   10.2.3.1 Hydrolytic Ring‐Openings of Epoxides......Page 373
   10.2.3.2 Ring‐Openings of Epoxides by Nucleophiles Other than Water......Page 376
   10.2.4.1 Hydrovinylations......Page 378
   10.2.4.2 Hydroborations......Page 381
  10.2.5 Cross‐coupling Reactions......Page 383
  10.2.6 Miscellaneous Reactions......Page 386
  10.3.1 [2+1] Cycloadditions......Page 390
   10.3.2.1 (Hetero)‐Diels–Alder Cycloadditions......Page 399
   10.3.2.2 1,3‐Dipolar Cycloadditions......Page 400
   10.3.2.3 Other Cycloadditions......Page 403
  10.3.3 Cyclisations Through Domino Reactions......Page 406
  10.3.4 Miscellaneous Cyclisations......Page 410
 10.4 Conclusions......Page 415
 Abbreviations......Page 416
 References......Page 417
 11.2 Cobalt‐Mediated Reactions of Carbon‐Centred Radicals......Page 437
  11.2.1 Homocoupling Reactions......Page 438
  11.2.2 Cross‐coupling Reactions......Page 440
  11.2.3 Additions to Alkenes and Alkynes......Page 443
  11.2.4 Cyclisation Reactions......Page 445
  11.2.5 Dehalogenation......Page 449
  11.2.6 Oxidation......Page 451
  11.2.7 Acylation......Page 453
  11.2.8 Applications of Cobalt Complexes in Photoredox Catalysis......Page 455
  11.2.9 Miscellaneous Reactions......Page 458
  11.3.1 Nitrogen‐Centred Radicals......Page 460
  11.3.2 Other Types of Radicals......Page 461
 11.4 Overview and Conclusion......Page 462
  11.5.1 Synthesis of Chloro(pyridine)cobaloxime Co(dmgH)2Cl(py) (116)......Page 463
  11.5.2 Synthesis of Aqua(cyano)heptamethyl Cobyrinate (56b)-Hydrophobic Vitamin B12 Model......Page 464
 Abbreviations......Page 465
 References......Page 466
Index......Page 473
EULA......Page 483