Modern Allene Chemistry

1153 Pages·2004·12.87 MB·English

by  Norbert Krause

ModernAlleneChemistry
Editedby
NorbertKrauseandA.StephenK.Hashmi
ModernAlleneChemistry.EditedbyN.KrauseandA.S.K.Hashmi
Copyright(cid:25)2004WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:3-527-30671-4
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Modern Allene Chemistry
Volume 1
Edited by
Norbert Krause and A. Stephen K. Hashmi
Editors & AllbookspublishedbyWiley-VCHarecarefullypro-
duced.Nevertheless,authors,editors,andpublisher
ProfessorDr.NorbertKrause donotwarranttheinformationcontainedinthese
UniversityofDortmund books,includingthisbook,tobefreeoferrors.
OrganicChemistryII Readersareadvisedtokeepinmindthatstatements,
Otto-Hahn-Strasse6 data,illustrations,proceduraldetailsorotheritems
44227Dortmund mayinadvertentlybeinaccurate.
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(cid:25)2004WILEY-VCHVerlagGmbH&Co.KGaA,
Weinheim
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ISBN 3-527-30671-4
V
Contents
Volume 1
I SynthesisofAllenes 1
1 SynthesisofAllenesbyIsomerizationReactions 3
A.StephenK.Hashmi
1.1 Introduction 3
1.2 PrototropicRearrangementsandRelatedReactionsofAlkynes 6
1.2.1 HydrogenAtomsorAlkylGroupsasSubstituents 6
1.2.2 AlkenylorArylGroupsasSubstituents 9
1.2.3 AlkinylGroupsasSubstituents 12
1.2.4 CarbonylGroupsasSubstituents 13
1.2.5 HalogensasSubstituents 17
1.2.6 OxygenastheSubstituent 19
1.2.7 NitrogenastheSubstituent 21
1.2.8 SulfurastheSubstituent 23
1.2.9 SilylandStannylSubstituents 25
1.2.10 PhosphorusastheSubstituent 26
1.2.11 AllenesfromPrototropicIsomerizationsofAlkynesasReactive
Intermediates 27
1.3 SigmatropicRearrangements 27
1.3.1 [2,3]-SigmatropicRearrangements 27
1.3.2 [3,3]-SigmatropicRearrangements 29
1.4 RearrangementsofOtherSystemswithatLeastTwop-Bonds 33
1.5 Retro-EneReactions 33
1.6 ElectrocyclicRingOpenings 34
1.7 IntramolecularConjugateAdditions 34
1.8 ComplexReactionsandRearrangements 35
1.9 Conclusion 36
ModernAlleneChemistry.EditedbyN.KrauseandA.S.K.Hashmi
Copyright82004WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:3-527-30671-4
VI Contents
2 Metal-MediatedSynthesisofAllenes 51
AnjaHoffmann-R(cid:21)derandNorbertKrause
2.1 Introduction
2.2 Copper-MediatedSynthesisofAllenes 52
2.2.1 SubstitutionReactions 52
2.2.2 AdditionReactions 61
2.3 Lithium-,Magnesium-andZinc-MediatedSynthesisofAllenes 70
2.4 Aluminum-andIndium-MediatedSynthesisofAllenes 75
2.5 Titanium-andSamarium-MediatedSynthesisofAllenes 79
2.6 Conclusion 87
3 TransitionMetal-CatalyzedSynthesisofAllenes 93
MasamichiOgasawaraandTamioHayashi
3.1 Introduction 93
3.2 FormationofAllenesbySubstitutionReactions 93
3.2.1 S 2¢SubstitutionofPropargylCompounds 93
N
3.2.2 S 2¢Substitutionof2-Halo-1,3-ButadienesandRelated
N
Compounds 112
3.2.3 S 2¢SubstitutionofPent-2-en-4-ynylAcetates 117
N
3.2.4 S 2¢SubstitutionofPropargyl–MetalSpecies 118
E
3.3 FormationofAllenesbyAdditionReactions 121
3.3.1 1,4-AdditiontoConjugatedEnynesandRelatedReactions 121
3.3.2 1,6-ConjugateAdditiontoEnynylcarbonylCompounds 128
3.4 FormationofAllenesbyEliminationReactions 129
3.5 OtherMiscellaneousMethodsofPreparingAllenes 131
3.6 Formationof1,2,3-Butatrienes 133
3.7 Conclusion 136
4 EnantioselectiveSynthesisofAllenes 141
HiroakiOhno,YasuoNagaoka,andKiyoshiTomioka
4.1 Introduction 141
4.2 ChiralityTransferfromPropargylicCompounds 141
4.2.1 Organocopper-MediatedAlkylationofPropargylAlcohol
Derivatives 141
4.2.2 Copper-MediatedHalogenationofPropargylAlcoholDerivatives 148
4.2.3 RearrangementofPropargylAlcoholDerivatives 152
4.2.4 Palladium(0)-CatalyzedReactionsofPropargylAlcoholDerivatives 155
4.2.5 S 2¢ReductionofPropargylAlcoholDerivatives 158
N
4.2.6 Ring-OpeningReactionsofPropargylEpoxidesandRelated
Compounds 160
4.2.7 ChiralPropargyl–orAllenyl–MetalReagents 163
Contents VII
4.3 EliminationReactionsofChiralAllylicCompounds 165
4.3.1 ChiralityTransferfromAllylicPosition 165
4.3.2 EliminationReactionsofAllylicCompoundsHavingaChiralLeaving
Group 168
4.4 SynthesisofAllenesUsingChiralReagents 169
4.4.1 AsymmetricDeprotonation–Protonation 169
4.4.2 AsymmetricHorner–Wadsworth–EmmonsandRelatedReactions 171
4.5 DirectAsymmetricSynthesisofAllenesUsinganExternalChiral
Catalyst 171
4.6 SynthesisofAllenesUsingInternalChiralAuxiliaries 175
4.7 KineticResolution 175
4.8 Conclusion 177
II SpecialClassesofAllenes 183
5 AllenicHydrocarbons–PreparationandUseinOrganicSynthesis 185
HenningHopf
5.1 Introduction 185
5.2 AllenicHydrocarbonsfromSimpleBuildingBlocks 186
5.3 PreparationofAllenicHydrocarbons 188
5.3.1 GeneralMethods 188
5.3.2 Alkylallenes 190
5.3.3 Vinylallenes 194
5.3.4 Ethynylallenes 197
5.3.5 ConjugatedBisallenes 199
5.3.6 Cyclopropylallenes 202
5.3.7 Arylallenes 204
5.3.8 AllenesCarryingOtherUnsaturatedSubstituents 209
5.3.9 SemicyclicAllenicHydrocarbons 217
5.4 AllenicHydrocarbonsasReactionIntermediates 218
5.5 WhyAllenicHydrocarbonsAreofInterestinPreparativeOrganic
Chemistry 222
6 CyclicAllenesUptoSeven-MemberedRings 243
ManfredChristl
6.1 Introduction 243
6.2 Three-,Four-andFive-MemberedRings 245
6.3 Six-MemberedRings 248
6.3.1 Unsubstituted1,2-Cyclohexadiene 248
6.3.2 Substituted1,2-Cyclohexadienes 260
6.3.3 BridgedandAnnulated1,2-Cyclohexadienes 266
6.3.4 1,2,4-Cyclohexatriene,3d2-1H-NaphthaleneandTheirDerivatives 272
6.3.5 HeterocyclicDerivativesof1,2,4-Cycloheptatriene(162)and
3d2-1H-Naphthalene(221) 289
VIII Contents
6.3.6 HeterocyclicDerivativesof1,2-Cyclohexadiene(6) 299
6.4 Seven-MemberedRings 324
6.4.1 1,2-CycloheptadieneandItsSimpleDerivatives 325
6.4.2 1,2,4,6-CycloheptatetraeneandItsSimpleDerivatives 332
6.4.3 AnnulatedandBridgedDerivativesof1,2-Cycloheptadiene 349
6.4.4 HeterocyclicDerivativesof1,2-Cycloheptadiene 350
7 Acceptor-SubstitutedAllenes 359
KlausBanertandJensLehmann
7.1 Introduction 359
7.2 SynthesisofAcceptor-SubstitutedAllenes 360
7.2.1 MethodswithBuildingUpoftheCarbonSkeletonoftheAllene 360
7.2.2 PrototropicIsomerizationofPropargylCompounds 361
7.2.3 [2,3]-SigmatropicRearrangementofPropargylCompounds 364
7.2.4 OtherRearrangementReactions 367
7.2.5 NucleophilicSubstitutionofPropargylCompounds 369
7.2.6 Palladium-CatalyzedCarbonylationofPropargylCompounds 371
7.2.7 1,4-AdditiontoEnynes 373
7.2.8 EliminationandCleavageReactions 373
7.2.9 IntroductionoftheAcceptorSubstituentintotheAllene 375
7.2.10 SynthesisfromOtherAcceptor-SubstitutedAllenes 378
7.3 ReactionsofAcceptor-SubstitutedAllenes 379
7.3.1 NucleophilicAddition 379
7.3.2 NucleophilicAdditionIncludingRingClosure 386
7.3.3 ElectrophilicAddition 390
7.3.4 RingClosuretoFormCarbocycles 392
7.3.5 RingClosuretoProduceHeterocycles 395
7.3.6 Diels–AlderReactions 401
7.3.7 OtherCycloadditionReactions 406
7.3.8 SigmatropicRearrangementReactions 411
7.3.9 OtherRearrangementReactions 414
7.3.10 MiscellaneousReactions 415
7.4 Conclusion 416
8 Donor-SubstitutedAllenes 425
ReinholdZimmerandHans-UlrichReissig
8.1 Introduction 425
8.2 O-SubstitutedAllenes 427
8.2.1 SynthesisofO-SubstitutedAllenes 427
8.2.2 DeprotonationofAlkoxyallenesandReactionwithElectrophiles–
Ring-ClosingReactions 431
8.2.3 CycloadditionsandCyclizations 449
8.2.4 FormationofAcetalsandSubsequentMetathesisReactions 458
8.2.5 MiscellaneousReactionsofO-SubstitutedAllenes 462
Contents IX
8.3 N-SubstitutedAllenes 467
8.3.1 SynthesisofN-SubstitutedAllenes 467
8.3.2 ReactionsofN-SubstitutedAllenes 471
8.4 S-andSe-SubstitutedAllenes 475
8.4.1 SynthesisofS-SubstitutedAllenes 475
8.4.2 ReactionsofS-SubstitutedAllenes 478
8.4.3 SynthesisandReactionsofSe-SubstitutedAllenes 484
8.5 Conclusion 485
9 SynthesisandReactionsofAllenylmetalCompounds 493
JamesA.Marshall,BenjaminW.Gung,andMelissaL.Grachan
9.1 Introduction 493
9.1.1 Preparation 493
9.1.2 ReactionCharacteristics 494
9.2 AllenyllithiumReagents 497
9.2.1 Structure 497
9.2.2 RegioselectivityofSilylation 500
9.3 AllenylcopperReagents 508
9.4 AllenylmagnesiumHalides 509
9.5 AllenylboronReagents 510
9.6 AllenyltitaniumReagents 517
9.7 Allenylsilanes 527
9.8 Allenylstannanes 543
9.8.1 AllenyltinHalideReagents 543
9.8.2 TrialkylallenyltinReagents 546
9.8.3 ReactionsofChiralAllenyltinReagents 548
9.8.4 SynthesisandReactionsofChiralAllenyltinHalides 551
9.8.5 ChiralCatalysis 554
9.8.6 OxygenatedAllenyltinHalides 555
9.8.7 IntramolecularAdditions 556
9.9 AllenylpalladiumReagents 558
9.9.1 Synthesis 558
9.9.2 Cross-CouplingReactions 559
9.9.3 Decarboxylation 561
9.9.4 Carbonylation 562
9.9.5 CyclizationsandCascadeReactions 563
9.10 AllenylzincReagents 565
9.10.1 RacemicAllenylzincReagents 566
9.10.2 EnantioenrichedChiralAllenylzincReagents 568
9.11 AllenylindiumReagents 574
9.11.1 Metal–HalogenExchange 576
9.11.2 ChiralLewisAcids 584
9.12 MiscellaneousAllenylmetalReagents 585