Computational Methods in Organometallic Catalysis: From Elementary Reactions to Mechanisms 1st Editio

642 Pages·2021·20.25 MB·english

by  by Yu Lan (Author)

ComputationalMethodsinOrganometallicCatalysis
Computational Methods in Organometallic
Catalysis
From Elementary Reactions to Mechanisms
Yu Lan
Author AllbookspublishedbyWiley-VCHarecarefully
produced.Nevertheless,authors,editors,and
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10 9 8 7 6 5 4 3 2 1
v
Contents
Foreword xv
Preface xvii
PartI TheoreticalViewofOrganometallicCatalysis 1
1 IntroductionofComputationalOrganometallicChemistry 3
1.1 OverviewofOrganometallicChemistry 3
1.1.1 GeneralViewofOrganometallicChemistry 3
1.1.2 ABriefHistoryofOrganometallicChemistry 6
1.2 UsingComputationalTooltoStudytheOrganometallicChemistry
Mechanism 8
1.2.1 MechanismofTransitionMetalCatalysis 8
1.2.2 MechanisticStudyofTransitionMetalCatalysisbyTheoretical
Methods 10
References 13
2 ComputationalMethodsinOrganometallicChemistry 19
2.1 IntroductionofComputationalMethods 19
2.1.1 TheHistoryofQuantumChemistryComputationalMethods 19
2.1.2 Post-HFMethods 21
2.2 DensityFunctionalTheory(DFT)Methods 23
2.2.1 OverviewofDensityFunctionalTheoryMethods 23
2.2.2 Jacob’sLadderofDensityFunctionals 25
2.2.3 TheSecondRungin“Jacob’sLadder”ofDensityFunctionals 25
2.2.4 TheThirdRungin“Jacob’sLadder”ofDensityFunctionals 26
2.2.5 TheFourthRungin“Jacob’sLadder”ofDensityFunctionals 26
2.2.6 TheFifthRungin“Jacob’sLadder”ofDensityFunctionals 26
2.2.7 CorrectionofDispersionInteractioninOrganicSystems 27
2.3 BasisSetandItsApplicationinMechanismStudies 29
2.3.1 GeneralViewofBasisSet 29
2.3.2 Pople’sBasisSets 30
2.3.3 PolarizationFunctions 31
vi Contents
2.3.4 DiffuseFunctions 31
2.3.5 Correlation-ConsistentBasisSets 31
2.3.6 PseudoPotentialBasisSets 32
2.4 SolventEffect 33
2.5 HowtoChooseaMethodinComputationalOrganometallic
Chemistry 34
2.5.1 WhyDFTMethodIsChosen 34
2.5.2 HowtoChooseaDensityFunctional 34
2.5.3 HowtoChooseaBasisSet 36
2.6 RevealingaMechanismforAnOrganometallicReactionbyTheoretical
Calculations 37
2.7 OverviewofPopularComputationalPrograms 37
2.8 TheLimitationofCurrentComputationalMethods 40
2.8.1 TheAccuracyofDFTMethods 40
2.8.2 ExactSolvationEffect 41
2.8.3 EvaluationofEntropyEffect 41
2.8.4 TheComputationofExcitedStateandHighSpinState 41
2.8.5 SpeculationontheReactionMechanism 41
References 42
3 ElementaryReactionsinOrganometallicChemistry 51
3.1 GeneralViewofElementaryReactionsinOrganometallicChemistry 51
3.2 CoordinationandDissociation 52
3.2.1 CoordinationBondandCoordination 52
3.2.2 Dissociation 55
3.2.3 LigandExchange 57
3.3 OxidativeAddition 59
3.3.1 ConcertedOxidativeAddition 60
3.3.2 Substitution-typeOxidativeAddition 62
3.3.3 Radical-typeAddition 67
3.3.4 OxidativeCyclization 68
3.4 ReductiveElimination 70
3.4.1 ConcertedReductiveElimination 71
3.4.2 Substitution-typeReductiveElimination 73
3.4.3 Radical-Substitution-typeReductiveElimination 74
3.4.4 BimetallicReductiveElimination 75
3.4.5 EliminativeReduction 78
3.5 Insertion 78
3.5.1 1,2-Insertion 79
3.5.2 1,1-Insertion 80
3.5.3 ConjugativeInsertion 83
3.5.4 Outer-SphereInsertion 84
3.6 Elimination 86
3.6.1 β-Elimination 86
3.6.2 α-Elimination 90
Contents vii
3.7 Transmetallation 92
3.7.1 ConcertedRing-TypeTransmetallation 92
3.7.2 TransmetallationThroughElectrophilicSubstitution 98
3.7.3 StepwiseTransmetallation 99
3.8 Metathesis 100
3.8.1 σ-BondMetathesis 100
3.8.2 OlefinMetathesis 102
3.8.3 AlkyneMetathesis 106
References 106
PartII OntheMechanismofTransition-metal-assisted
Reactions 125
4 TheoreticalStudyofNi-Catalysis 127
4.1 Ni-MediatedC—HBondActivation 128
4.1.1 Ni-MediatedAreneC—HActivation 128
4.1.2 Ni-MediatedAldehydeC—HActivation 132
4.2 Ni-MediatedC—HalogenBondCleavage 133
4.2.1 ConcertedOxidativeAdditionofC—HalogenBond 133
4.2.2 Radical-TypeSubstitutionofC—HalogenBond 135
4.2.3 C—HalogenBondCleavagebyβ-HalideElimination 137
4.2.4 NucleophilicSubstitutionofC—HalogenBond 139
4.3 Ni-MediatedC—OBondActivation 140
4.3.1 EtherC—OBondActivation 140
4.3.2 EsterC—OBondActivation 142
4.4 Ni-MediatedC—NBondCleavage 148
4.5 Ni-MediatedC—CBondCleavage 151
4.5.1 C—CSingleBondActivation 151
4.5.2 C=CDoubleBondActivation 152
4.6 Ni-MediatedUnsaturatedBondActivation 153
4.6.1 OxidativeCyclizationwithUnsaturatedBonds 153
4.6.2 ElectrophilicAdditionofUnsaturatedBonds 156
4.6.3 UnsaturatedCompoundsInsertion 157
4.6.4 NucleophilicAdditionofUnsaturatedBonds 159
4.7 Ni-MediatedCyclization 160
4.7.1 Ni-MediatedCycloadditions 161
4.7.2 Ni-MediatedRingSubstitutions 163
4.7.3 Ni-MediatedRingExtensions 166
References 168
5 TheoreticalStudyofPd-Catalysis 181
5.1 Pd-CatalyzedCross-couplingReactions 182
5.1.1 Suzuki–MiyauraCoupling 183
5.1.2 NegishiCoupling 186
viii Contents
5.1.3 StilleCoupling 189
5.1.4 HiyamaCoupling 190
5.1.5 Heck–MizorokiReaction 192
5.2 Pd-MediatedC—HeteroBondFormation 196
5.2.1 C—BBondFormation 196
5.2.2 C—SBondFormation 197
5.2.3 C—IBondFormation 200
5.2.4 C—SiBondFormation 201
5.3 Pd-MediatedC—HActivationReactions 204
5.3.1 Chelation-FreeC(sp3)—HActivation 206
5.3.2 Chelation-FreeC(sp2)—HActivation 208
5.3.3 CoordinativeChelation-Assistedortho-C(aryl)—HActivation 210
5.3.4 CovalentChelation-Assistedortho-C(aryl)—HActivation 212
5.3.5 Chelation-Assistedmeta-C(aryl)—HActivation 214
5.3.6 CoordinativeChelation-AssistedC(sp3)—HActivation 216
5.3.7 CovalentChelation-AssistedC(sp3)—HActivation 216
5.3.8 C—HBondActivationThroughElectrophilicDeprotonation 219
5.3.9 C—HBondActivationThroughσ-Complex-AssistedMetathesis 221
5.3.10 C—HBondActivationThroughOxidativeAddition 223
5.4 Pd-MediatedActivationofUnsaturatedMolecules 224
5.4.1 AlkeneActivation 225
5.4.2 AlkyneActivation 225
5.4.3 EnyneActivation 226
5.4.4 ImineActivation 229
5.4.5 COActivation 229
5.4.6 IsocyanideActivation 231
5.4.7 CarbeneActivation 231
5.5 AllylicPdComplex 234
5.5.1 FormationfromAllylicOxidativeAddition 235
5.5.2 FormationfromAllylicNucleophilicSubstitution 236
5.5.3 FormationfromtheNucleophilicAttackontoAllene 237
5.5.4 FormationfromAllylicC—HActivation 237
5.5.5 FormationfromAlleneInsertion 238
References 239
6 TheoreticalStudyofPt-Catalysis 257
6.1 MechanismofPt-CatalyzedC—HActivation 258
6.1.1 OxidativeAdditionofC—HBond 259
6.1.2 ElectrophilicDehydrogenation 259
6.1.3 CarbeneInsertionintoC—HBonds 261
6.2 MechanismofPt-CatalyzedAlkyneActivation 264
6.2.1 NucleophilicAdditions 264
6.2.2 Cyclopropanation 266
6.2.3 OxidativeCycloaddition 268
6.3 MechanismofPt-CatalyzedAlkeneActivation 270
Contents ix
6.3.1 HydroaminationofAlkenes 270
6.3.2 HydroformylationofAlkenes 272
6.3.3 IsomerizationofCyclopropenes 273
References 274
7 TheoreticalStudyofCo-Catalysis 289
7.1 Co-MediatedC—HBondActivation 289
7.1.1 HydroarylationofAlkenes 291
7.1.2 HydroarylationofAllenes 293
7.1.3 HydroarylationofAlkynes 294
7.1.4 HydroarylationofNitrenoid 296
7.1.5 OxidativeC—HAlkoxylation 297
7.2 Co-MediatedCycloadditions 297
7.2.1 Co-MediatedPauson–KhandReaction 298
7.2.2 Co-Catalyzed[4+2]Cyclizations 299
7.2.3 Co-Catalyzed[2+2+2]Cyclizations 299
7.2.4 Co-Catalyzed[2+2]Cyclizations 300
7.3 Co-CatalyzedHydrogenation 301
7.3.1 HydrogenationofCarbonDioxide 301
7.3.2 HydrogenationofAlkenes 304
7.3.3 HydrogenationofAlkynes 306
7.4 Co-CatalyzedHydroformylation 307
7.4.1 DirectHydroformylationbyH andCO 308
2
7.4.2 TransferHydroformylation 309
7.5 Co-MediatedCarbeneActivation 310
7.5.1 ArylationofCarbene 310
7.5.2 CarboxylationofCarbene 312
7.6 Co-MediatedNitreneActivation 313
7.6.1 AziridinationofOlefins 314
7.6.2 AminationofIsonitriles 314
7.6.3 AminationofC—HBonds 315
References 317
8 TheoreticalStudyofRh-Catalysis 329
8.1 Rh-MediatedC—HActivationReactions 330
8.1.1 Rh-CatalyzedArylationofC—HBond 330
8.1.2 Rh-CatalyzedAlkylationofC—HBond 332
8.1.3 Rh-CatalyzedAlkenylationofC—HBond 335
8.1.4 Rh-CatalyzedAminationofC—HBond 338
8.1.5 Rh-CatalyzedHalogenationofC—HBond 340
8.2 Rh-CatalyzedC—CBondActivationsandTransformations 341
8.2.1 Strain-drivenOxidativeAddition 341
8.2.2 TheCarbon—CyanoBondActivation 342
8.2.3 β-CarbonElimination 343
8.3 Rh-MediatedC—HeteroBondActivations 343
x Contents
8.3.1 C—NBondActivation 344
8.3.2 C—OBondActivation 345
8.4 Rh-CatalyzedAlkeneFunctionalizations 345
8.4.1 HydrogenationofAlkene 346
8.4.2 DiborationofAlkene 347
8.5 Rh-CatalyzedAlkyneFunctionalizations 349
8.5.1 HydroacylationofAlkynes 349
8.5.2 HydroaminationofAlkynes 349
8.5.3 HydrothiolationofAlkynes 351
8.5.4 HydroacetoxylationofAlkynes 351
8.6 Rh-CatalyzedAdditionReactionsofCarbonylCompounds 352
8.6.1 HydrogenationofKetones 352
8.6.2 HydrogenationofCarbonDioxide 353
8.6.3 HydroacylationofKetones 353
8.7 Rh-CatalyzedCarbeneTransformations 354
8.7.1 CarbeneInsertionintoC—HBonds 354
8.7.2 ArylationofCarbenes 357
8.7.3 CyclopropanationofCarbenes 358
8.7.4 CyclopropenationofCarbenes 359
8.8 Rh-CatalyzedNitreneTransformations 359
8.8.1 NitreneInsertionintoC—HBonds 360
8.8.2 AziridinationofNitrenes 361
8.9 Rh-CatalyzedCycloadditions 362
8.9.1 (3+2)Cycloadditions 365
8.9.2 Pauson–Khand-type(2+2+1)Cycloadditions 367
8.9.3 (5+2)Cycloadditions 367
8.9.4 (5+2+1)Cycloadditions 369
References 369
9 TheoreticalStudyofIr-Catalysis 387
9.1 Ir-CatalyzedHydrogenations 387
9.1.1 HydrogenationofAlkenes 388
9.1.2 HydrogenationofCarbonylCompounds 391
9.1.3 HydrogenationofImines 393
9.1.4 HydrogenationofQuinolines 396
9.2 Ir-CatalyzedHydrofunctionalizations 397
9.2.1 Ir-CatalyzedHydroaminations 397
9.2.2 Ir-CatalyzedHydroarylations 397
9.2.3 Ir-CatalyzedHydrosilylations 399
9.3 Ir-CatalyzedBorylations 401
9.3.1 BorylationofAlkanes 402
9.3.2 BorylationofArenes 403
9.4 Ir-CatalyzedAminations 405
9.4.1 AminationofAlcohols 405
9.4.2 AminationofArenes 407
Contents xi
9.5 Ir-CatalyzedC—CBondCouplingReactions 407
References 409
10 TheoreticalStudyofFe-Catalysis 419
10.1 Fe-MediatedOxidations 420
10.1.1 AlkaneOxidations 420
10.1.2 AreneOxidations 422
10.1.3 AlkeneOxidations 423
10.1.4 OxidativeCatecholRingCleavage 425
10.2 Fe-MediatedHydrogenations 426
10.2.1 HydrogenationofAlkenes 427
10.2.2 HydrogenationofCarbonyls 429
10.2.3 HydrogenationofImines 430
10.2.4 HydrogenationofCarbonDioxide 430
10.3 Fe-MediatedHydrofunctionalizations 431
10.3.1 HydrosilylationofKetones 431
10.3.2 HydroaminationofAllenes 432
10.4 Fe-MediatedDehydrogenations 434
10.4.1 DehydrogenationofAlcohols 434
10.4.2 DehydrogenationofFormaldehyde 435
10.4.3 DehydrogenationofFormicAcid 435
10.4.4 DehydrogenationofAmmonia-Borane 437
10.5 Fe-CatalyzedCouplingReactions 438
10.5.1 C—CCross-CouplingswithArylHalide 438
10.5.2 C—NCross-CouplingswithArylHalide 438
10.5.3 C—CCross-CouplingswithAlkylHalide 441
10.5.4 Iron-MediatedOxidativeCoupling 441
References 441
11 TheoreticalStudyofRu-Catalysis 451
11.1 Ru-MediatedC—HBondActivation 452
11.1.1 MechanismoftheRu-MediatedC—HBondCleavage 452
11.1.2 Ru-CatalyzedC—HBondArylation 456
11.1.3 Ru-Catalyzedortho-AlkylationofArenes 460
11.1.4 Ru-Catalyzedortho-AlkenylationofArenes 461
11.2 Ru-CatalyzedHydrogenations 464
11.2.1 HydrogenationofAlkenes 464
11.2.2 HydrogenationofCarbonyls 465
11.2.3 HydrogenationofEsters 466
11.2.4 HydrodefluorinationofFluoroarenes 467
11.3 Ru-CatalyzedHydrofunctionalizations 468
11.3.1 Hydroacylations 469
11.3.2 Hydrocarboxylations 470
11.3.3 Hydroborations 471
11.4 Ru-MediatedDehydrogenations 472