上海有機所有機合成課件

有機合成反應(yīng)金屬有機化學(xué)國家重點實驗室E-mail:tangy@Shanghai,China方法考試

重要性Shanghai,China中間體產(chǎn)物的形成官能團簡介Shanghai,China烯烴的反應(yīng)-立體化學(xué)特性Shanghai,China第一章烯烴的反應(yīng)Shanghai,ChinaRepresentativeCis-AdditionProcesses烯烴的反應(yīng)-立體化學(xué)特性§1-1IntroductionShanghai,ChinaRepresentativeTrans-AdditionProcesses烯烴的反應(yīng)-立體化學(xué)特性Shanghai,China烯烴的反應(yīng)-立體化學(xué)特性Shanghai,China烯烴的反應(yīng)-烯烴構(gòu)象分析D.Kim&Co-workers,TetrahedronLett.1986,27,943.§1-2ConformationsofOlefinicSubstratesShanghai,China烯烴的反應(yīng)-烯烴構(gòu)象分析Butaneversus1-ButeneShanghai,China1-butene2-propen-1-olE(kcal/mol)-180-900(Deg)90180543210Conformstoabinitio(3-21G)values:Wiberg,K.B.;Martin,E.J.Am.Chem.Soc.1985,107,5035.E(kcal/mol)-180-900(Deg)90180543210烯烴的反應(yīng)-烯烴構(gòu)象分析A-1,2interactionsShanghai,China2-methyl-1-butene2-methyl-2-propen-1-olE(kcal/mol)E(kcal/mol)543210543210-180-900(Deg)90180-180-900(Deg)90180烯烴的反應(yīng)-烯烴構(gòu)象分析A-1,2interactionsShanghai,China-180-900(Deg)90180-180-900(Deg)90180E(kcal/mol)E(kcal/mol)543210543210ValuescalculatedusingMM2(molecularmechanics)forcefieldsviatheMacromodelmulticonformationsearch.(Z)-2-pentene(Z)-2-buten-1-ol烯烴的反應(yīng)-烯烴構(gòu)象分析A-1,3interactionsShanghai,China-180-900(Deg)90180543210E(kcal/mol)(Z)-2-hydroxy-3-penteneTheTorsionalEnergyProfile烯烴的反應(yīng)-烯烴構(gòu)象分析A-1,3interactionsShanghai,China烯烴的反應(yīng)-烯烴構(gòu)象分析A-1,3interactionsShanghai,China烯烴的反應(yīng)-基本反應(yīng)§1-3OlefinHydroborationShanghai,ChinaShanghai,China烯烴的反應(yīng)-基本反應(yīng)Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

RepresetativeHydroborationExamples:AcyclicControlShanghai,China烯烴的反應(yīng)-基本反應(yīng)

RepresetativeHydroborationExamples:AcyclicControlShanghai,China烯烴的反應(yīng)-基本反應(yīng)

RepresetativeHydroborationExamples:CyclicControlShanghai,China§1-4OlefinEpoxidation烯烴的反應(yīng)-基本反應(yīng)

Cis-selectivityShanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China

StericEffects

Howdoweaccountforthehighexoselectivitiesinadditionreactionstonorbornene?Highlyexoselectiveforelectrophilic,nucleophilicandcycloadditionreactionsRateenhancementduetostrainSchleyer,P.R.J.Amer.Chem.Soc.1967,89,701.AdditionfromexofaceavoidseclipsingA&Bhydrogens(betterhyperconjugativestabilizationoftransitionstate)烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China

AssociativeSubstrate-ReagentInteractions:directedreaction烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaDiastereoselectivePeracidEpoxidation烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaTheSharplessEpoxidationShanghai,ChinaEpoxidationofAcyclicAlcohol烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaEpoxidationofAcyclicHomoallylicAlcohols烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaEpoxidationofAcyclicHomoallylicAlcohols烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaNewMethodsJACS2000,8317.烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaScience2001,1140烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaDioxiraneEpoxidation烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Houk,JACS1997,12982.Shanghai,China§1-5OlefinHydrogenationRelevantReviewarticles:Angew.Chem.Int.Edit.26,190-203(1987).Historically,primarystereochemicalcontroldesignedaroundanalysisofstericenvironmentinvicinityofC=C.烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaHowever,theinfluenceofpolareffectswasdocumentedThompson,J.Org.Chem.36,2577(1971)烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaPolarfunctionalgroupsmayplayaroleincontrollingthediastereoselectivityofthehydrogenationprocess;however,thecontrolelementswerenotwell-defined.J.E.McMurryetal.TetrahedronLett..3731(1970)烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaThefirstrationalattempttoidentifythoseFGswhichwilldirectthereactionH.ThopsonJACS1973,95,838.烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaThefirstrationalattempttoassociatecatalystwithsubstrateH.ThopsonJACS1974,96,6232.烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaCationicHydrogenationCatalysts烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaMechanismofHydrogenationCationicRhodium-(I)Catalysts.烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaMechanismofHydrogenationCationicRhodium-(I)Catalysts.ThatHatomlyingparalleltothepi-system(HA)shouldmigratepreferentiallyifthedihydrideisanintermediate.烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaPolarfunctionalgroupsotherthanOHmayalsodirecttheprocess烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,China烯烴的反應(yīng)-基本反應(yīng)

Shanghai,ChinaHomoallylicAlcoholsEvans,MorrisseyTetrahedronLett.266005(1985)Shanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,China§1-6OlefinBromination-1§1-6-1IntroductionShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,China§1-7OlefinOxymercuration-1Shanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,ChinaProblemsoftheday:Shanghai,ChinaShanghai,ChinaShanghai,China§1-7RelatedOlefinAdditionRxns:HalogenElectrophilesShanghai,ChinaShanghai,ChinaShanghai,ChinaRelatedOlefinAdditionRxnsShanghai,ChinaAllenes:

multi-reactionsite

chiralityHydrohalogenationReactionsofAllenesShanghai,ChinaMaetal.Pure&Appl.2001,73,337.Shanghai,ChinaShanghai,ChinaShanghai,ChinaShanghai,China§1-8TheSimmons-SmithReactionShanghai,ChinaShanghai,ChinaJACS,2003,12990.Shanghai,ChinaShanghai,China§1-9Conjugateaddition烯烴的反應(yīng)