Modern Organocopper Chemistry

392 Pages·2002·6.613 MB·English

by  Norbert Krause (editor)

ModernOrganocopperChemistry.EditedbyNorbertKrause
Copyright>2002Wiley-VCHVerlagGmbH
ISBNs:3-527-29773-1(Hardcover);3-527-60008-6(Electronic)
EditedbyN.Krause
ModernOrganocopper
Chemistry
ModernOrganocopperChemistry.EditedbyNorbertKrause
Copyright>2002Wiley-VCHVerlagGmbH
ISBNs:3-527-29773-1(Hardcover);3-527-60008-6(Electronic)
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ModernOrganocopperChemistry.EditedbyNorbertKrause
Copyright>2002Wiley-VCHVerlagGmbH
ISBNs:3-527-29773-1(Hardcover);3-527-60008-6(Electronic)
Edited by Norbert Krause
Modern Organocopper Chemistry
ModernOrganocopperChemistry.EditedbyNorbertKrause
Copyright>2002Wiley-VCHVerlagGmbH
ISBNs:3-527-29773-1(Hardcover);3-527-60008-6(Electronic)
Editor 9 Thisbookwascarefullyproduced.
Nevertheless,editor,authorsandpublisher
Prof.Dr.N.Krause donotwarranttheinformationcontained
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OrganicChemistryII advisedtokeepinmindthatstatements,
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Germany otheritemsmayinadvertentlybe
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ModernOrganocopperChemistry.EditedbyNorbertKrause
Copyright>2002Wiley-VCHVerlagGmbH
ISBNs:3-527-29773-1(Hardcover);3-527-60008-6(Electronic)
v
Foreword
Copper is one of the oldest transition metals to be used in synthetic organic
chemistry. Starting in the 60’s, organocopper reagents became among the most
popularsynthetictoolsinthetotalsynthesisofnaturalproduct.Thisisduetothe
ease of handling and to the chemo-, regio- and stereoselectivities attained with
these reagents. Their unique properties for the conjugate addition, for the clean
S 2 substitution, for the mild opening of epoxides, for the carbometallation of
N
triple bonds, etc ... makes them unavoidable reagents for these synthetic trans-
formations.
Overtheyears,awholefamilyofreagentsevolvedwithincreasedselectivityand
reactivity. ‘‘Homocuprates’’, ‘‘heterocuprates’’, ‘‘higher order cuprates’’, ‘‘mixed
cuprates’’, and others, are terms often employed, and a newcomer chemist may
worry about their different properties. Despite a lot of progress in the area of
organocopperchemistrythereisstillastronglackofknowledgeinthemechanistic
insights. No reactive intermediates have been trapped, and this ‘‘black box’’ was
only considered through analogies with other closely related transition metals or,
morerecently,throughextensivecalculations.Thisistosaythatallourknowledge
about organocopper chemistry did not came by rational design but through em-
piricalwaywithexperimentation.
Overtheyears,severalreviewarticlesappearedonorganocopperchemistry.Most
often, they cover some aspects or some restricted class of reagents, and they are
addressed to chemists knowing already the main reactions of organocopper re-
agents. In contrast to other transition metals, such as Pd, Ni, Rh etc ... only few
books, covering the entire area of organocopper chemistry, have been published.
Thepresentbookisthemostcomprehensiveandallthemostrecentadvancesare
extensively discussed: Zn-Cu reagents, Sn and Si-Cu reagents, H-Cu reagents,
asymmetric reactions. The reader will learn about the structure of organocopper
reagentsandaboutthemostupdatedmechanisticbeliefspresentlyknown.
Organocopper chemistry is of wide applicability, very efficient and easy to per-
form. The main problem is to know the most appropriate reagent to use. The
reader will find in this book all the details for the reagent of choice, for the scope
and limitations, for the type of substrate needed. This book should be helpful not
onlytoadvancedresearchchemists,butalsoforteachingthischemistrytoyounger
vi Foreword
students inacomprehensive andmodernway.Suchawidecoverageofanimpor-
tantpieceofchemistryisnotonlywelcome;itwasneeded!
December2001
ProfessorAlexandreAlexakis
UniversityofGeneva
Geneva
ModernOrganocopperChemistry.EditedbyNorbertKrause
Copyright>2002Wiley-VCHVerlagGmbH
ISBNs:3-527-29773-1(Hardcover);3-527-60008-6(Electronic)
vii
Contents
Foreword v
Preface xi
ListofAuthors xiii
1 StructuresandReactivitiesofOrganocopperCompounds 1
JohannT.B.H.Jastrzebski,GerardvanKoten
1.1 Introduction 1
1.1.1 HistoricalPerspective 1
1.1.2 TheOxidationStatesofCopper 3
1.1.3 ThermalStabilityandBondinginOrganocopper(I)Compounds 6
1.2 HomolepticOrganocopperCompoundsCunRn 8
1.3 HeterolepticOrganocopperCompoundsCunBmRnXm 17
1.4 Organocuprates 26
1.4.1 NeutralHomolepticandHeterolepticOrganocuprates 27
1.4.2 AnionicHomolepticandHeterolepticOrganocuprates 32
1.4.3 Lower-andHigher-orderCyanocuprates 34
1.5 ConcludingRemarks 37
Acknowledgement 40
References 40
2 TransmetalationReactionsProducingOrganocopperReagents 45
PaulKnochel,BodoBetzemeier
2.1 Introduction 45
2.2 TransmetalationofFunctionalizedOrganolithiumandOrganomagnesium
Reagents 45
2.3 TransmetalationofOrganoboronandOrganoaluminiumReagents 51
2.4 TransmetalationofFunctionalizedOrganozincReagents 54
2.4.1 PreparationofOrganozincReagents 54
2.4.1.1 PreparationofOrganozincHalides 56
2.4.1.2 PreparationofDiorganozincReagents 59
2.4.2 SubstitutionReactionswithCopper-ZincReagents 62
2.4.3 AdditionReactionswithCopper-ZincReagents 65
2.5 TransmetalationofOrganotin,Organosulfur,andOrganotellurium
Reagents 67
viii Contents
2.6 TransmetalationofOrganotitaniumandOrganomanganeseReagents 70
2.7 TransmetalationofOrganozirconiumandOrganosamariumReagents 71
2.8 Conclusion 74
References 75
3 Heteroatomcupratesanda-HeteroatomalkylcupratesinOrganicSynthesis 79
R.KarlDieter
3.1 Introduction 79
3.2 Heteroatomcuprates 80
3.2.1 GroupIVAHeteroatoms(Si,Ge,Sn) 80
3.2.1.1 ConjugateAdditionReactions 83
3.2.1.2 SilylcuprationandStannylcuprationofAlkynesandAllenes 93
3.2.1.3 SubstitutionReactions 102
3.2.2 GroupVAandVIAHeteroatoms(N,O,P) 108
3.3 a-Heteroatomalkylcuprates 109
3.3.1 GroupVIHeteroatoms(O,S,Se) 110
3.3.2 GroupVHeteroatoms(N,P)andSilicon 114
3.3.3 a-Fluoroalkylcupratesanda-Fluoroalkenylcuprates 122
3.4 Non-transferableHeteroatom(alkyl)cupratesanda-
Heteroatomalkylcuprates 123
3.4.1 SimpleResidualLigands 124
3.4.2 ChiralLigands 127
3.5 Summary 133
Acknowledgments 134
References 134
4 Copper-mediatedAdditionandSubstitutionReactionsofExtendedMultiple
BondSystems 145
NorbertKrause,AnjaHoffmann-Ro¨der
4.1 Introduction 145
4.2 Copper-mediatedAdditionReactionstoExtendedMichaelAcceptors 146
4.2.1 Acceptor-substitutedDienes 146
4.2.2 Acceptor-substitutedEnynes 150
4.2.3 Acceptor-substitutedPolyenynes 159
4.3 Copper-mediatedSubstitutionReactionsofExtendedSubstrates 160
4.4 Conclusion 162
References 163
5 Copper(I)-mediated1,2-and1,4-Reductions 167
BruceH.Lipshutz
5.1 IntroductionandBackground 167
5.2 MoreRecentDevelopments:StoichiometricCopperHydrideReagents 168
5.3 1,4-ReductionsCatalyticinCu(I) 174
5.4 1,2-ReductionsCatalyzedbyCopperHydride 179
5.5 HeterogeneousCuH-CatalyzedReductions 182
5.6 OverviewandFutureDevelopments 184
References 185
Contents ix
6 Copper-mediatedDiastereoselectiveConjugateAdditionandAllylicSubstitution
Reactions 188
BernhardBreit,PeterDemel
Abstract 188
6.1 ConjugateAddition 188
6.1.1 StereocontrolinCyclicDerivatives 188
6.1.2 StereocontrolinAcyclicDerivatives 192
6.1.2.1 g-Heteroatom-substitutedMichaelAcceptors 192
6.1.2.2 g-Alkyl-substituteda,b-UnsaturatedCarbonylDerivatives 198
6.1.2.3 a,b-UnsaturatedCarbonylDerivativeswithStereogenicCentersin
Positionsotherthantheg-Position 200
6.1.2.4 DirectedConjugateAdditionReactions 200
6.1.3 Auxiliary-boundChiralMichaelAcceptorsandAuxiliaryChiralMetal
Complexes 202
6.2 AllylicSubstitution 210
References 218
7 Copper-catalyzedEnantioselectiveConjugateAdditionReactionsofOrganozinc
Reagents 224
BenL.Feringa,RobertNaasz,RosalindeImbos,LeggyA.Arnold
7.1 Introduction 224
7.2 OrganozincReagents 227
7.3 Copper-catalyzed1,4-Addition 229
7.3.1 Phosphoramidite-basedCatalysts 229
7.3.2 CatalyticCycle 233
7.3.3 VariationofLigands 234
7.3.4 CyclicEnones 239
7.3.5 2-Cyclopentenone 240
7.3.6 AcyclicEnones 242
7.4 SyntheticApplications 243
7.4.1 TandemConjugateAddition-AldolReactions 243
7.4.2 KineticResolutionof2-Cyclohexenones 243
7.4.3 Sequential1,4-Additionsto2,5-Cyclohexadienones 246
7.4.4 Lactones 250
7.4.5 Nitroalkenes 250
7.4.6 AnnulationMethodology 252
7.5 Conclusions 254
Acknowledgements 255
ReferencesandNotes 255
8 Copper-MediatedEnantioselectiveSubstitutionReactions 259
A.SofiaE.Karlstro¨m,Jan-ErlingBa¨ckvall
8.1 Introduction 259
8.2 AllylicSubstitution 261
8.2.1 AllylicSubstrateswithChiralLeavingGroups 262
8.2.2 ChiralAuxiliarythatisCleavedoffaftertheReaction 268