N-杂环卡宾催化选择性有机反应的新进展-蔡小华

檵檵檵檵檵檵檵檵檵檵殝殝殝殝N－*550025N-NHC、NHC、。、NHC。N-O621A1000-0518201302-0123-11DOI10．3724/SP．J．1095．2013．203062012-07-102012-08-22209620062012204Tel/[e-mail]-NHCArduengo11991NHCNHC2-3。NHC。NHC。NHC、4-7。20NHC、NHC、NHC、、。NHC、。1N-N-、、、Scheme1。N-Csp26CσCNpCpCσN-Scheme1GeneraltypesofN-heterocycliccarbene302Vol．30Iss．220132CHINESEJOURNALOFAPPLIEDCHEMISTRYFeb．2013NCNCN。N-N-Scheme2a。Scheme2、CO2。Scheme2FormationofN-heterocycliccarbene2。2010HoHe8NHCⅡ12-α-Scheme3。TESOTf12-4--1-70%68%Scheme4。DBUSingh9NHC2TosNαβ-83%～95%26--4-Scheme5。Scheme3Catalyticintermoleculartail-to-tailhydroalkenylationofstyreneswithα-olefinsScheme4Anetholeandindenet-thetero-hydroalkenylationwithanα-olefin2011Glorius10NHCRh2+Scheme6。NHC3NHC499∶1。5678-er94∶6。42130Scheme5ExpeditioussynthesisoffunctionalizedpiperidinesScheme6Ligand-controlledhighlyregioselectiveandasymmetrichydrogenationofquinoxalinesZhao11NHC5LewisH。、、TBAFScheme7。Scheme7Chemo-andregioselectivehydrosilylationofcarbonylderivatives3NHC。2010Scheidt12NHC6Lewisαβ-αβ-cis20∶197%～99%eeScheme8。134-LewisTiOi-Pr4NHC。Scheme8Highlystereoselectiveannulationreactionswithhomoenolates201113NHCRh2+75+2Scheme9。55%～94%3．1．03．1．0。Ye5212N-14NHC812-Michael4+122--3-Scheme10。stetter、aldol3。Scheme9Diastereoselectivetandemhetero-5+2cycloaddition/claisenrearrangementreactionScheme10Diastereoselectivesynthesisof3-hydroxyindanones4NHCNHCNHCNHC。4．1NHC2009Scheidt15NHC9α-N-TsMannichRβ-、β-Scheme11。β-、β-、β-Scheme12。Scheme11EnantioselectiveMannichreactionswithα-aryloxyacetaldehydesScheme12EnantioselectiveMannichreactionswithα-aryloxyacetaldehydesusingtrappingreagentsZhang16NHC10N-Tos、N-N-StaudingerSβScheme13。53%～78%ee97%。NHCScheme141762130ee95%。200918NHC4+2334-34-Scheme15Scheme16。Scheme13HighlyenantioselectivesynthesisofN-Bocβ-lactamsScheme14AsymmetricesterificationofketenesScheme15EnantioselectivesynthesisofdihydrocoumarinsScheme16Proposedcatalyticcycle2011Jian19NHC1011N-2+2Scheme17。NHC。Cheng20NHCScheme18NHC12。NHC13S。Enders21NHC14Scheme197212N-Scheme17Enantioselectiveformal2+2cycloadditionofketenesandN-sulfinylanilinesScheme18N-Heterocycliccarbenecatalyzedreactionofphthalaldehydesee99%。NHC15αβ-Stetter14-22ee90%～99%Scheme20。Scheme19Asymmetriccross-benzoinreactionsScheme20AsymmetricintermolecularStetterreactions2009Rovis23NHC1613-αβ-Scheme21。MichaelNHC。2011NHC17Brnstedαβ-Rγ-ee99%93%Scheme2224。Scheme21Asymmetricsynthesisoffunctionalizedcyclopentanones2011Zhu25NHC1813-αβ-ee82130Scheme22Asymmetricsynthesisoftrans-γ-lactams98%Scheme23。αβ-αβ-DBU。Scheme23Annulationofαβ-unsaturatedaldehydeswith13-dicarbonylsBiswas26DBUNHC19αβ-Scheme24。NHCee99%dr10∶1。Scheme24Enantioselectivecyclopropanationofenals4．2NHCNHCNHC．O2。2007Montgomery27NHC20-15-Scheme25αβ-。Scheme25Asymmetricnickel-catalyzedaldehyde/alkynereductivecouplings2011Selim28NHC219212N-α-Scheme26γ。Scheme26Asymmetricγ-selectivityallylicarylationofaliphaticallylicbromidesLeeHoveyda29NHC22αβ-βScheme27。NHC-Cu-arylNHC-Cu-alkenylαβ-63%～97%47%～97%ee。--TASF。Scheme27Conjugateadditionsofaryl-andalkenylsilylfluoridestoayclicenones2010LewisacidLindsayMcArthur30NHC2375%85%eeScheme28。Yang315%NHCⅠ2416-Scheme29。Scheme28AsymmetricreductionofketonesScheme29AsymmetricFriedel-Crafts/cyclizationreactionNHC。2009Shi32NHCPd2+25N-TosScheme30。Nαα-。N-Tosee5%～65%33。03130Scheme30EnantioselectivearylationofN-tosylarylimineswitharylboronicacids2008Shi34NHC2613-Scheme31。ee62%～91%。2011Liu35NHC27TMEDA-PdMe2α-33-ee98%Scheme32。Scheme31AsymmetricdiaminationofconjugateddienesandtrieneScheme32Enantioselectiveintramolecularα-arylationofamidesC—C。Rovis36NHC28m-DNBα-Sα-Scheme33。C—HH2C—C。Scheme33Catalyticasymmetricα-acylationoftertiaryamines5N-、。N-1312N-。NHC、、NHC、、NHCNHCNHCN-NHC、。1ArduengoAJHarlowRLKilneM．AStableCrystallineCarbeneJ．JAmChemSoc19911131361-363．2SUNXiaoyuWUJie．N-HeterocyclicCarbeneAVersatileOrganocataIystJ．ChineseJOrgChem2006266745-756inChinese．．N-J．2006266745-756．3FortmanGCNolanSP．N-HeterocyclicCarbeneNHCLigandsandPalladiuminHomogeneousCross-CouplingCatalysisAPerfectUnionJ．ChemSocRev201140105151-5169．4SunWYChowALFLiXHetal．LuminescentCyclometalatedPlatinumⅡComplexesContainingN-HeterocyclicCarbeneLigandswithPotentinVitroandinVivoAnti-CancerPropertiesAccumulateinCytoplasmicStructuresofCancerCellsJ．ChemSci201124728-736．5LiuWKBensdorfKHagenbachAetal．SynthesisandBiologicalStudiesofSilverN-HeterocyclicCarbeneComplexesDerivedfrom45-DiarylimidazoleJ．EurJMedChem201146125927-5934．6RubbianRCanSZKitanovicIetal．ComparativeinVitroEvaluationofN-HeterocyclicCarbeneGoldⅠComplexesoftheBenzimidazolylideneTypeJ．JMedChem201154248646-8657．7MercsLAlbrechtM．BeyondCatalysisN-HeterocyclicCarbeneComplexesasComponentsforMedicinalLuminescentandFunctionalMaterialsApplicationsJ．ChemSocRev20103961903-1912．8HoCYHeL．CatalyticIntermolecularTail-to-TailHydroalkenylationofStyreneswithα-OlefinsRegioselectiveMigratoryInsertionControlledbyaNickel/N-HeterocyclicCarbeneJ．AngewChemIntEd201049489182-9186．9SinghSRaiVKSinghPetal．ExpeditiousSynthesisofFunctionalizedPiperidinesbyRegioselectiveRingOpeningofAziridinesbyEnalsCatalyzedbyanN