Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials (Volume 1 and 2), Second Edition

711 Pages·2011·6.75 MB·English

Edited by
Dennis G. Hall
Boronic Acids
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Edited by Dennis G. Hall
Boronic Acids
Volume 2
Preparation and Applications in Organic Synthesis,
Medicine and Materials
Second Completely Revised Edition
With a Foreword by Akira Suzuki
TheEditors AllbookspublishedbyWiley-VCHarecarefully
produced.Nevertheless,authors,editors,and
Prof.DennisG.Hall publisherdonotwarranttheinformationcontained
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InterdisciplinaryScience errors.Readersareadvisedtokeepinmindthat
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V
Foreword
Hydroboration,discoveredin1956,hasmadeorganoboranesreadilyavailable.This
discoveryopenedthegatetoanewcontinentforthechemicalcommunitytoexplore,
develop, and exploit. Mainly in the late-1960s and 1970s, many novel types of
carbon–carbon and carbon–heteroatom bondforming reactions of organoboranes
werediscoveredanddevelopedforuseinorganicsynthesis.
Thepalladium-catalyzedcross-couplingoforganoboroncompoundswithorganic
electrophilessuchasorganichalidesinthepresenceofbasewasdevelopedin1979.
Overthepast30yearsorso,transitionmetal-catalyzedcross-couplingreactionsof
boronicacidderivativeshaveemergedasoneofthemostimportantandwidelyused
organometallic reactions for carbon–carbon and carbon–heteroatom bond forma-
tion,andisnowregardedasanintegralpartofanysyntheticroutetowardbuilding
complexorganicchemicals.Thecouplingreactionhasmanyadvantages:thereac-
tantsarereadilyavailable,nontoxic,andair-andwater-stable,andtheyreactunder
mildconditionsandareamenabletoavarietyofreactionconditions,includingthe
use of aqueous solvents. Moreover, the inorganic boron byproduct can be easily
removedafterthereaction.Mostimportantofall,thecouplingproceedswithhigh
regio- and stereoselectivity, and is little affected by steric hindrance. The process
doesnotaffectotherfunctionalgroupsinthemoleculeandcanthusbeusedinone-
potstrategies.Inaddition,thereactionhasprovedtobeextremelyversatile.Conse-
quently, thesecoupling reactions have been actively utilized not only in academic
laboratoriesbutalsoinindustrialprocesses,likeinpharmaceuticalandagrochem-
icalindustriesaswellasotherindustriesfortheproductionofliquidcrystalsand
organicLEDs.
Today, the use of boronic acid derivatives and their applications continue to
evolvewithmanynewfindingsreportedduringthepastdecade.Forexample,new
reactions, catalysts and ligands have been developed. Increasingly, industry is
seeking to use more environment-friendly processes. These often require inge-
nious solutions to which Suzuki coupling is well suited. We can expect to see
manymoreinterestingversionsofthecouplingreactionsandotherapplications
ofboronicacidsinthefuture.
HokkaidoUniversity,Sapporo,Japan AkiraSuzuki
VII
Contents to Volume 1
Foreword V
Contents to Volume 2 XIII
Preface XV
List of Contributors XIX
1 Structure,Properties,andPreparationofBoronicAcidDerivatives:
OverviewofTheirReactionsandApplications 1
DennisG.Hall
1.1 IntroductionandHistoricalBackground 1
1.2 StructureandPropertiesofBoronicAcidDerivatives 2
1.2.1 GeneralTypesandNomenclatureofBoronicAcidDerivatives 2
1.2.2 BoronicAcids 3
1.2.2.1 StructureandBonding 3
1.2.2.2 PhysicalPropertiesandHandling 8
1.2.2.3 SafetyConsiderations 9
1.2.2.4 AcidicCharacter 9
1.2.2.5 ChemicalStability 12
1.2.3 BoronicAcidDerivatives 15
1.2.3.1 Boroxines(CyclicAnhydrides) 15
1.2.3.2 BoronicEsters 16
1.2.3.3 Acyloxy-andDiacyloxyboronates 25
1.2.3.4 DialkoxyboranesandOtherHeterocyclicBoranes 25
1.2.3.5 DiboronylEsters 26
1.2.3.6 AzaborolidinesandOtherBoron–NitrogenHeterocycles 27
1.2.3.7 DihaloboranesandDihydroalkylboranes 29
1.2.3.8 Trifluoro-andTrihydroxyborateSalts 30
1.3 PreparationofBoronicAcidsandTheirEsters 31
1.3.1 ArylboronicAcids 31
1.3.1.1 ElectrophilicTrappingofArylmetalIntermediateswithBorates 31
1.3.1.2 TransmetalationofArylSilanesandStannanes 41
VIII Contents
1.3.1.3 CouplingofArylHalideswithDiboronylReagents 42
1.3.1.4 DirectBoronationbyTransitionMetal-CatalyzedAromaticC–H
Functionalization 43
1.3.1.5 CycloadditionsofAlkynylboronates 43
1.3.1.6 OtherMethods 43
1.3.2 DiboronicAcids 44
1.3.3 HeterocyclicBoronicAcids 44
1.3.4 AlkenylboronicAcids 45
1.3.4.1 ElectrophilicTrappingofAlkenylmetalIntermediateswithBorates 45
1.3.4.2 TransmetalationMethods 45
1.3.4.3 TransitionMetal-CatalyzedCouplingbetweenAlkenylHalides/
TriflatesandDiboronylReagents 45
1.3.4.4 HydroborationofAlkynes 55
1.3.4.5 AlkeneMetathesis 58
1.3.4.6 DiboronylationandSilaborationofUnsaturatedCompounds 59
1.3.4.7 OtherMethods 60
1.3.5 AlkynylboronicAcids 60
1.3.6 AlkylboronicAcids 61
1.3.7 AllylicBoronicAcids 63
1.3.8 ChemoselectiveTransformationsofCompoundsContaining
aBoronicAcid(Ester)Substituent 63
1.3.8.1 OxidativeMethods 64
1.3.8.2 ReductiveMethods 64
1.3.8.3 GenerationandReactionsofa-Boronyl-Substituted
CarbanionsandRadicals 66
1.3.8.4 Reactionsofa-HaloalkylboronicEsters 68
1.3.8.5 OtherTransformations 70
1.3.8.6 ProtectionofBoronicAcidsforOrthogonalTransformations 72
1.4 IsolationandCharacterization 73
1.4.1 RecrystallizationandChromatography 74
1.4.2 SolidSupportsforBoronicAcidImmobilizationandPurification 75
1.4.2.1 DiethanolaminomethylPolystyrene 75
1.4.2.2 OtherSolid-SupportedDiolResins 76
1.4.2.3 SolubleDiolApproaches 76
1.4.3 AnalyticalandSpectroscopicMethodsforBoronicAcidDerivatives 76
1.4.3.1 MeltingPoints,CombustionAnalysis,andHPLC 76
1.4.3.2 MassSpectrometry 77
1.4.3.3 NuclearMagneticResonanceSpectroscopy 77
1.4.3.4 OtherSpectroscopicMethods 78
1.5 OverviewoftheReactionsofBoronicAcidDerivatives 78
1.5.1 MetalationandMetal-CatalyzedProtodeboronation 78
1.5.2 OxidativeReplacementofBoron 79
1.5.2.1 Oxygenation 79
1.5.2.2 AminationandAmidation 81
1.5.2.3 Halodeboronation 81
1.5.3 Carbon–CarbonBondFormingProcesses 85
Contents IX
1.5.3.1 TransitionMetal-CatalyzedCross-CouplingwithCarbon
HalidesandSurrogates(Suzuki–MiyauraCross-Coupling) 85
1.5.3.2 TransitionMetal-CatalyzedInsertions,Cycloisomerizations,and
C–HFunctionalizationsBasedonTransmetalationofBoronicAcids 88
1.5.3.3 Heck-TypeCouplingtoAlkenesandAlkynes 90
1.5.3.4 Rhodium-andOtherTransitionMetal-CatalyzedAdditionsto
Alkenes,CarbonylCompounds,andImineDerivatives 90
1.5.3.5 Diol-CatalyzedAdditionsofBoronicEsterstoUnsaturated
CarbonylCompoundsandAcetals 92
1.5.3.6 AllylationofCarbonylCompoundsandImineDerivatives 93
1.5.3.7 UncatalyzedAdditionsofBoronicAcidstoIminesandIminiums 93
1.5.4 Carbon–HeteroatomBondFormingProcesses 94
1.5.4.1 Copper-CatalyzedCouplingwithNucleophilicOxygen
andNitrogenCompounds 94
1.5.5 OtherReactions 94
1.6 OverviewofOtherApplicationsofBoronicAcidDerivatives 97
1.6.1 UseasReactionPromotersandCatalysts 97
1.6.2 UseasProtectingGroupsforDiolsandDiamines 99
1.6.3 UseasSupportsforImmobilization,Derivatization,Affinity
Purification,AnalysisofDiols,Sugars,andGlycosylatedProteins
andCells 100
1.6.4 UseasReceptorsandSensorsforCarbohydratesandOther
SmallMolecules 102
1.6.5 UseasAntimicrobialAgentsandEnzymeInhibitors 103
1.6.6 UseinNeutronCaptureTherapyforCancer 105
1.6.7 UseinTransmembraneTransport 105
1.6.8 UseinBioconjugationandLabelingofProteinsandCellSurface 106
1.6.9 UseinChemicalBiology 107
1.6.10 UseinMaterialsScienceandSelf-Assembly 108
References 109
2 Metal-CatalyzedBorylationofC–HandC–HalogenBondsof
Alkanes,Alkenes,andArenesfortheSynthesisofBoronicEsters 135
TatsuoIshiyamaandNorioMiyaura
2.1 Introduction 135
2.2 BorylationofHalidesandTriflatesviaCouplingofH–BandB–B
Compounds 137
2.2.1 BorylationofArylHalidesandTriflates 138
2.2.2 AlkenylHalidesandTriflates 143
2.2.3 AllylicHalides,AllylicAcetates,andAllylicAlcohols 145
2.2.4 BenzylicHalides 148
2.3 BorylationviaC–HActivation 148
2.3.1 AliphaticC–HBonds 148
2.3.2 AlkenylC–HBonds 151
2.3.3 AromaticC–HBonds 153
2.4 CatalyticCycle 159
X Contents
2.5 Summary 161
References 161
3 TransitionMetal-CatalyzedElement-BorylAdditionstoUnsaturated
OrganicCompounds 171
MichinoriSuginomeandToshimichiOhmura
3.1 Introduction 171
3.2 Diboration 172
3.2.1 DiboronReagentsforDiboration 172
3.2.2 DiborationofAlkynes 173
3.2.3 DiborationofAlkenes,Allenes,1,3-Dienes,and
Methylenecyclopropanes 176
3.2.4 SyntheticApplicationsofDiborationProducts 183
3.3 Silaboration 185
3.3.1 SilylboraneReagentsforSilaboration 185
3.3.2 SilaborationofAlkynes 187
3.3.3 SilaborationofAlkenes,Allenes,1,3-Dienes,and
Methylenecyclopropanes 191
3.3.4 SyntheticApplicationofSilaborationProducts 200
3.4 Carboboration 202
3.4.1 DirectAddition:CyanoborationandAlkynylboration 203
3.4.2 TransmetalativeCarboboration 205
3.5 MiscellaneousElement-BorylAdditions 207
3.6 Conclusion 208
References 208
4 TheContemporarySuzuki–MiyauraReaction 213
CoryValenteandMichaelG.Organ
4.1 Introduction 213
4.1.1 PreambleandOutlook 213
4.1.2 ABriefHistory 214
4.1.3 MechanisticAspects 214
4.2 DevelopmentsMadeintheCouplingofNontrivialSubstrates 215
4.2.1 RationalDesignofLigandsforUseintheSuzuki–Miyaura
Reaction 215
4.2.1.1 OrganophosphineLigandsandProperties 217
4.2.1.2 N-HeterocyclicCarbeneLigandsandtheirProperties 219
4.2.2 TheSuzuki–MiyauraCross-CouplingofChallengingArylHalides 220
4.2.2.1 OverviewofChallenges 220
4.2.2.2 Organophosphine-DerivedCatalysts 221
4.2.2.3 NHC-DerivedCatalysts 228
4.2.3 TheSuzuki–MiyauraReactionInvolvingUnactivatedAlkylHalides 234
4.2.3.1 AssociatedDifficulties 234
4.2.3.2 Cross-CouplingsPromotedbyPhosphinesandAmine-Based
Ligands 235
Contents XI
4.2.3.3 Cross-Coupling-PromotedNHCLigands 240
4.3 AsymmetricSuzuki–MiyauraCross-Couplings 241
4.3.1 AchievingAxialChiralityintheSuzuki–MiyauraReaction 241
4.3.1.1 AxialChiralityInducedbyChiralLigands/Catalysts 241
4.3.1.2 AxialChiralityInducedbyPointChirality 244
4.3.1.3 AxialChiralityInducedbyPlanarChirality 246
4.3.2 AchievingPointChiralityintheSuzuki–MiyauraReaction 246
4.4 IterativeSuzuki–MiyauraCross-Couplings 248
4.4.1 orthoMetalation–Cross-couplingIterations 248
4.4.2 Triflating–Cross-CouplingIterations 248
4.4.3 IterativeCross-CouplingsviaOrthogonalReactivity 249
4.4.3.1 BifunctionalElectrophiles 249
4.4.3.2 BifunctionalOrganoboranes 252
4.5 ConclusionsandFutureOutlook 256
References 257
5 Rhodium-andPalladium-CatalyzedAsymmetricConjugateAdditions
ofOrganoboronicAcids 263
GuillaumeBerthon-GellozandTamioHayashi
5.1 Introduction 263
5.2 Rh-CatalyzedEnantioselectiveConjugateAdditionofOrganoboron
Reagents 263
5.2.1 a,b-UnsaturatedUnsaturatedKetones 264
5.2.1.1 AShortHistory 264
5.2.1.2 Mechanism 264
5.2.1.3 ModelforEnantioselection 266
5.2.1.4 OrganoboronSourcesOtherThanBoronicAcids 266
5.2.1.5 RhPrecatalysts 269
5.2.1.6 LigandSystems 269
5.2.1.7 a,b-UnsaturatedAldehydes 278
5.2.2 EnantioselectiveAdditiontoa,b-UnsaturatedEstersandAmides 279
5.2.2.1 DiastereoselectiveConjugateAddition 282
5.2.2.2 FumarateandMaleimides 284
5.2.2.3 SyntheticallyUsefulAcceptors 286
5.2.2.4 ConjugateAdditionsofBorylandSilylGroups 286
5.2.3 AdditiontoOtherElectron-DeficientAlkenes 288
5.2.3.1 ArylmethyleneCyanoacetates 288
5.2.3.2 Alkenylphosphonates 288
5.2.3.3 Nitroalkene 288
5.2.3.4 Sulfones 289
5.2.3.5 Additiontocis-AllylicAlcohols 291
5.2.3.6 1,4-Addition/EnantioselectiveProtonation 291
5.2.4 1,6-ConjugateAdditions 294
5.2.5 Rh-CatalyzedEnantioselectiveConjugateAdditionwithOther
OrganometallicReagents 296