上海有机所有机合成.ppt

Shanghai,China,有机合成反应,唐勇金属有机化学国家重点实验室,E-mail:tangy,Shanghai,China,方法考试,重要性,Shanghai,China,中间体产物的形成官能团,简介,Shanghai,China,烯烃的反应-立体化学特性,FunctionalGroup,Shanghai,China,烯烃的反应-立体化学特性,Shanghai,China,第一章烯烃的反应,Shanghai,China,RepresentativeCis-AdditionProcesses,烯烃的反应-立体化学特性,1-1Introduction,Shanghai,China,烯烃的反应-立体化学特性,Shanghai,China,RepresentativeTrans-AdditionProcesses,烯烃的反应-立体化学特性,Shanghai,China,烯烃的反应-立体化学特性,Shanghai,China,烯烃的反应-烯烃构象分析,D.KimMartin,E.J.Am.Chem.Soc.1985,107,5035.,E(kcal/mol),-180-900(Deg)90180,543210,烯烃的反应-烯烃构象分析,A-1,2interactions,Shanghai,China,2-methyl-1-butene,2-methyl-2-propen-1-ol,E(kcal/mol),E(kcal/mol),543210,543210,-180-900(Deg)90180,-180-900(Deg)90180,烯烃的反应-烯烃构象分析,A-1,2interactions,Shanghai,China,Acetaldehydeexhibitsasimilarconformationalbias,烯烃的反应-烯烃构象分析,K.Houk,JACS1987,109,6591-6600.,Shanghai,China,-180-900(Deg)90180,-180-900(Deg)90180,E(kcal/mol),E(kcal/mol),543210,543210,ValuescalculatedusingMM2(molecularmechanics)forcefieldsviatheMacromodelmulticonformationsearch.,(Z)-2-pentene(Z)-2-buten-1-ol,烯烃的反应-烯烃构象分析,A-1,3interactions,Shanghai,China,-180-900(Deg)90180,543210,E(kcal/mol),(Z)-2-hydroxy-3-pentene,TheTorsionalEnergyProfile,烯烃的反应-烯烃构象分析,A-1,3interactions,Shanghai,China,烯烃的反应-烯烃构象分析,A-1,3interactions,Shanghai,China,烯烃的反应-烯烃构象分析,Review:Hoffman,R.W.Chem.Rev.1989,1841.,Shanghai,China,烯烃的反应-基本反应,1-3OlefinHydroboration,Shanghai,China,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,RepresetativeHydroborationExamples:AcyclicControl,Shanghai,China,烯烃的反应-基本反应,RepresetativeHydroborationExamples:AcyclicControl,Shanghai,China,烯烃的反应-基本反应,RepresetativeHydroborationExamples:CyclicControl,Shanghai,China,1-4OlefinEpoxidation,烯烃的反应-基本反应,Cis-selectivity,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,StericEffectsHowdoweaccountforthehighexoselectivitiesinadditionreactionstonorbornene?,Highlyexoselectiveforelectrophilic,nucleophilicandcycloadditionreactionsRateenhancementduetostrain,Schleyer,P.R.J.Amer.Chem.Soc.1967,89,701.,AdditionfromexofaceavoidseclipsingAhowever,thecontrolelementswerenotwell-defined.,J.E.McMurryetal.TetrahedronLett.3731(1970),烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,ThefirstrationalattempttoidentifythoseFGswhichwilldirectthereaction,H.ThopsonJACS1973,95,838.,烯烃的反应-基本反应,Shanghai,China,Thefirstrationalattempttoassociatecatalystwithsubstrate,H.ThopsonJACS1974,96,6232.,烯烃的反应-基本反应,Shanghai,China,CationicHydrogenationCatalysts,烯烃的反应-基本反应,Shanghai,China,MechanismofHydrogenationCationicRhodium-(I)Catalysts.,烯烃的反应-基本反应,Shanghai,China,MechanismofHydrogenationCationicRhodium-(I)Catalysts.,ThatHatomlyingparalleltothepi-system(HA)shouldmigratepreferentiallyifthedihydrideisanintermediate.,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,PolarfunctionalgroupsotherthanOHmayalsodirecttheprocess,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,烯烃的反应-基本反应,Shanghai,China,HomoallylicAlcoholsEvans,MorrisseyTetrahedronLett.266005(1985),Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,1-6OlefinBromination-1,1-6-1Introduction,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,1-7OlefinOxymercuration-1,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,Problemsoftheday:,Shanghai,China,Shanghai,China,Shanghai,China,1-7RelatedOlefinAdditionRxns:HalogenElectrophiles,Shanghai,China,Shanghai,China,Shanghai,China,RelatedOlefinAdditionRxns,Shanghai,China,Allenes:multi-reactionsitechirality,HydrohalogenationReactionsofAllenes,Shanghai,China,Maetal.Pure&Appl.2001,73,337.,Shanghai,China,Shanghai,China,Shanghai,China,Shanghai,China,1-8TheSimmons-SmithReaction,Shanghai,China,Shanghai,China,JACS,2003,12990.,Shanghai,China,Shanghai,China,1-9Conjugateaddition,烯烃的反应-基本反应,Michael,J.Prakt.Chem.1887,35,349.Michael,Am.Chem.J.1887,9,115.,Shanghai,China,CaseI,CaseII,1-9-1Introduction,Shanghai,China,Additiontoa,b-unsaturatedcompounds:Organoalkalimetalreagentsfromunstabilizedcarbanion:1,2-Enolateandotherstabilizedanion:1,4-Grignardreagents:1,2-(aldehyde),1,4-(Stericones),1,2-&1,4-mixtures(mostcases)Organocopperreagents:1,4-Lithiumdiorganocopperreagents:1,4-Cu(