Pauson-Khand Reaction: Scope, Variations and Applications, The

321 Pages·2012·11.52 MB·English

by  Ramon Rios Torres (edited by)

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The Pauson-Khand Reaction
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The Pauson-Khand
Reaction
Scope, Variations and Applications
Edited by
RAMON RIOS TORRES
Department of Organic Chemistry, University of Barcelona,
Barcelona, Spain and Catalan Institute of Research and Advanced
Studies (ICREA), Spain
A John Wiley & Sons, Ltd., Publication
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Thiseditionfirstpublished2012
©2012JohnWiley&Sons,Ltd
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LibraryofCongressCataloging-in-PublicationData
ThePauson-Khandreaction:scope,variations,andapplications/editedbyRamonRiosTorres.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-97076-8(hardback)
1.Pauson-Khandreaction. I.RiosTorres,Ramon.
QD281.R5P382012
547(cid:2).412–dc23
2011051669
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
ISBN:9780470970768(13digits)
Setin10/12ptTimesbyAptaraInc.,NewDelhi,India.
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Contents
ListofContributors xi
Foreword xiii
Preface xv
1. ThePauson-KhandReaction–anIntroduction 1
WilliamJ.Kerr
1.1 TheDiscoveryandEarlyEvolutionoftheKhandReaction 1
1.2 TheIntermolecularPauson-KhandReaction 4
1.2.1 RegioselectivityofAlkyneInsertion 5
1.2.2 RegioselectivityofAlkeneInsertion 6
1.3 TheIntramolecularPauson-KhandReaction 8
1.4 EnhancingthePauson-KhandAnnulationbyReactionPromotion 9
1.4.1 DryStateAdsorption 9
1.4.2 UltrasoundTechniques 10
1.4.3 MicrowavePromotion 10
1.4.4 AmineN-OxideAdditives 11
1.4.5 SulfidePromoters 13
1.5 CatalyticPauson-KhandProtocols 15
1.6 ConcludingRemarks 16
Acknowledgements 17
References 17
2. TheMechanismofthePauson-KhandReaction:Hypothesis,
ExperimentalFacts,andTheoreticalInvestigations 23
XacobeC.CambeiroandMiquelA.Perica`s
2.1 Introduction 23
2.2 StoichiometricPauson-KhandReaction 25
2.2.1 TheLigandSubstitutionSteps 25
2.2.2 CobaltacycleFormation 29
2.2.3 COInsertion 31
2.2.4 ReductiveElimination 32
2.3 CatalyticPauson-KhandReaction 32
2.4 TheoreticalStudies 33
2.4.1 GeneralApproachtotheMechanism 33
2.4.2 Regioselectivity.EarlyStepsofthePauson-KhandReaction 37
2.4.3 Stereoselectivity 41
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vi Contents
2.5 Conclusions 46
References 46
3. NonChiralPauson-KhandReaction 49
TakanoriShibata
3.1 HistoryofCo-MediatedPauson-KhandReaction 49
3.2 MechanismofthePauson-KhandReaction 50
3.3 AnEarlyExampleofCatalyticReaction 51
3.4 CatalyticReactionsbyAidofAdditives 52
3.5 CatalyticReactionUsingin-situGeneratedLow-ValentCobalt
Complex 55
3.6 CatalyticReactionUsingMultinuclearCobaltCarbonylCatalysts 59
3.7 CatalyticReactionUsingHeterogeneousCatalysts 61
3.8 CatalyticReactioninOtherThanConventionalSolvents 63
3.9 IntramolecularReactionofCarbodiimideswithAlkynes 65
References 66
4. DiastereoselectivePauson-KhandReactionusingChiralPoolTechniques
(ChiralSubstrates) 69
MartinKamlar,JanVesely,andRamonRiosTorres
4.1 IntroductionandBackground 69
4.2 IntramolecularDiastereoselectivePauson-KhandReaction 70
4.3 IntermolecularDiastereoselectivePauson-KhandReaction 87
4.4 Conclusion 90
References 91
5. AsymmetricIntra-andIntermolecularPauson-KhandReactions:The
ChiralAuxiliaryApproach 95
AlbertMoyano
5.1 Introduction 96
5.2 AsymmetricIntramolecularPKRswiththeAidofChiralAuxiliaries 99
5.2.1 ChiralAlkoxyacetylenes 99
5.2.2 ChiralAcetyleneThioethers 104
5.2.3 Chiral2-alkynoateDerivatives 106
5.2.4 ChiralO-alkylEnolEthers 108
5.2.5 Alkenylsulfoxides 113
5.2.6 AsymmetricIntramolecularPKRsMediatedbyChiral
AuxiliariesLocatedintheEnyneTether 114
5.3 AsymmetricIntermolecularPKRswiththeAidofChiralAuxiliaries 116
5.3.1 ChiralAlkoxyacetylenes 116
5.3.2 ChiralAcetyleneThioethers 124
5.3.3 AlkynylSulfoxides 125
5.3.4 ChiralYnaminesandYnamides 126
5.3.5 Chiral2-alkynoates 128
5.3.6 AlkenylSulfoxides 135
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Contents vii
5.4 ChiralReagentsfortheKineticResolutionofPKCycloadducts 138
5.5 Conclusion 140
Acknowledgements 140
References 140
6. TheEnantioselectivePauson-KhandReaction 147
Agust´ıLledo´,XavierVerdaguerandAntoniRiera
6.1 Introduction 148
6.2 MechanisticConsiderations.TopologyofAlkyne-DicobaltClusters 148
6.3 IntrinsicallyChiralDicobaltClusters 150
6.3.1 ResolutionofMonophosphineComplexes 150
6.3.2 SynthesisofChiralMonophosphineComplexesUsingChiral
N-Oxides 151
6.3.3 HeterobimetallicComplexes 151
6.4 ChiralPromoters 153
6.4.1 Sulfoxides 153
6.4.2 ChiralN-Oxides 153
6.5 ChiralLigands 155
6.5.1 Sulfides 155
6.5.2 Cyclopentadienes(Heterobimetallic) 156
6.5.3 C-ChiralandAxiallyChiralPhosphines 156
6.5.4 C -SymmetricBridgingBis-phosphines 161
2
6.5.5 C-ChiralBidentate(P,S)Ligands 162
6.5.6 S-ChiralBidentate(P,S)Ligands 167
6.6 SyntheticApplications 171
6.7 Conclusion 176
References 176
7. RecentAdvancementofCatalyticPauson-Khand-typeReactions 181
FukLoiLam,HangWaiLee,JunWangandFukYeeKwong
7.1 Introduction 181
7.2 Rhodium-CatalyzedPauson-Khand-TypeCyclizations 182
7.3 Iridium-CatalyzedPauson-Khand-TypeCyclizations 194
7.4 Titanium-CatalyzedPauson-Khand-TypeCyclizations 198
7.5 Ruthenium-CatalyzedPauson-Khand-TypeCyclizations 200
7.6 Nickel-andPalladium-CatalyzedPauson-Khand-TypeCyclizations 201
7.7 TandemReactionsandMiscellaneous(otherthanCocomplex) 204
7.8 Conclusion 206
Acknowledgements 206
References 206
8. RecentAdventureswiththePauson-KhandReactioninTotalSynthesis 211
ScottG.VanOrnum,SarahHoernerandJamesM.Cook
8.1 Introduction 212
8.2 (+)-Epoxydictymene 212
8.3 (±)-Pentaleneneand(-)-Pentalenene 214
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viii Contents
8.4 TheTandemPauson-KhandReactionDirectedTowardstheSynthesis
ofDicyclopentapentalenes 215
8.5 EnantioselectiveTotalSynthesisof(-)-(cid:2)-KainicAcid 219
8.6 TheTotalSynthesisofPaecilomycineA 220
8.7 TheTotalSynthesisof(+)-Achalensolide 221
8.8 TheTotalSynthesisof(-)-Alstonerine 222
8.9 TheTotalSynthesisof(±)-8(cid:2)-Hydroxystreptazolone 224
8.10 TheFormalTotalSynthesisof(±)-(cid:2)-and(cid:3)-Cedrene 226
8.11 AdditionalApplicationsofthePauson-KhandReaction
inTotalSynthesis 227
8.12 Conclusions 230
Acknowledgements 231
References 231
9. HeterogeneousCatalyticPauson-KhandReaction 239
YoungKeunChung
9.1 Introduction 240
9.2 DevelopmentofHeterogeneousCatalystsforPKR 240
9.2.1 Polymer-SupportedCatalyticSystems 241
9.2.2 BulkCobaltasaCatalyst 242
9.2.3 RaneyCobalt 243
9.2.4 MesoporousOrganizedZirconiumOxideSilicaPowders
asCatalyst 244
9.2.5 MesoporousGraphiticCarbonasaPromoter 245
9.3 TransitionMetalNanoparticleCatalyst 246
9.3.1 ColloidalCobaltNanoparticles 247
9.3.2 CobaltNanoparticlesonCharcoal 247
9.3.3 Poly(ethyleneglycol)-StabilizedCobaltNanoparticles 249
9.4 BimetallicNanoparticleCatalysts 250
9.4.1 ImmobilizedHeterobimetallicRu/CoNanoparticle 250
9.4.2 HeterobimetallicCo/RhNanoparticles 251
9.5 SequentialActionofTwoDifferentCatalystsinOne-PotReactions 261
9.5.1 ChiralPd(II)ComplexandBulkCobalton
Charcoal-CatalyzedTandemAsymmetricAllylicAlkylation
andPKAnnulationReactions 262
9.5.2 Pd(II)ComplexandCobaltNanoparticle-Catalyzed
Three-StepOne-PotSynthesisofFenestranes 262
9.5.3 PalladiumandCobaltNanoparticles-CatalyzedTandem
AllylicAlkylationandPKRs 264
9.6 Conclusion 265
References 266
10. OtherTransitionMetal-MediatedCyclizationsLeading
toCyclopentenones 275
RamonRiosTorresandJanVesely
10.1 IntroductionandBackground 276
10.2 [4+1]StrategiesfortheSynthesisofCyclopentenones 278
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Contents ix
10.3 [3+2]StrategiesfortheSynthesisofCyclopentenones 283
10.3.1 IronPromotedReactions 283
10.3.2 SynthesisofCyclopentenonesvia[3+2]Cycloadditionsof
FisherAlkenylComplexes 284
10.4 Nickel(0)andPalladium(0)SynthesisofCyclopentenones 285
10.5 MetalCarbineStrategiesfortheSynthesisofCyclopentenones 289
10.5.1 CyclopropylcarbeneChromiumComplexes 289
10.5.2 Rhodium(II)-CatalyzedStrategies 291
10.6 OtherMethodologies 292
10.7 Conclusions 298
Experimental 299
ReferencesandNotes 299
Index 307
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List of Contributors
Xacobe C. Cambeiro Institute of Chemical Research of Catalonia (ICIQ), Tarragona,
Spain
Young Keun Chung Department of Chemistry, College of Natural Sciences, Seoul Na-
tionalUniversity,Seoul,Korea
JamesM.CookDepartmentofChemistry,UniversityofWisconsin-Milwaukee,Milwau-
kee,Wisconsin,USA
SarahHoernerDepartmentofNaturalScience,ConcordiaUniversityWisconsin,Mequon,
Wisconsin,USA
Martin Kamlar Department of Organic and Nuclear Chemistry, Charles University in
Prague,Prague,CzechRepublic
William J. Kerr Department of Pure and Applied Chemistry, WestCHEM, Glasgow,
Scotland
Fuk Yee Kwong State Key Laboratory of Chirosciences and Department of Applied Bi-
ology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom,
Kowloon,HongKong
FukLoiLamStateKeyLaboratoryofChirosciencesandDepartmentofAppliedBiology
andChemicalTechnology,TheHongKongPolytechnicUniversity,HungHom,Kowloon,
HongKong
HangWaiLeeStateKeyLaboratoryofChirosciencesandDepartmentofAppliedBiology
andChemicalTechnology,TheHongKongPolytechnicUniversity,HungHom,Kowloon,
HongKong
Agust´ıLledo´ InstituteforResearchinBiomedicine(IRB)Barcelona,Barcelona,Spain
Albert Moyano Department of Organic Chemistry, University of Barcelona, Barcelona,
Spain
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xii ListofContributors
MiquelA.Perica`sInstituteofChemicalResearchofCatalonia(ICIQ),Tarragona,Spain
andDepartmentofOrganicChemistry,UniversityofBarcelona,Barcelona,Spain
AntoniRieraInstituteforResearchinBiomedicine(IRB)Barcelona,andDepartmentof
OrganicChemistry,UniversityofBarcelona,Barcelona,Spain
Ramon Rios Torres Department of Organic Chemistry, University of Barcelona, Spain,
andCatalanInstituteofResearchandAdvancedStudies(ICREA),Spain
TakanoriShibataDepartmentofChemistryandBiochemistry,WasedaUniversity,Okubo,
Shinjuku,Tokyo,Japan
JunWangStateKeyLaboratoryofChirosciencesandDepartmentofAppliedBiologyand
ChemicalTechnology,TheHongKongPolytechnicUniversity,HongKong
Scott G. Van Ornum Department of Natural Science, Concordia University Wisconsin,
Mequon,Wisconsin,USA
XavierVerdaguerInstituteforResearchinBiomedicine(IRB)Barcelona,andDepartment
ofOrganicChemistry,UniversityofBarcelona,Barcelona,Spain
JanVeselyDepartmentofOrganicandNuclearChemistry,CharlesUniversityinPrague,
Prague,CzechRepublic