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1、第七部分：实例讲解第七部分：实例讲解I.I.长叶烯的合成长叶烯的合成长叶烯的合成长叶烯的合成MeMeCH2MeMeStrategicbondandretro-MeCH2syntheticanalysisMeMeMeNotafusionpointMeMeMeeventhoughitisMea.HodisconnectionFusionina1,2-relationshipPointCH2CH2CH2b.KuodisconnectionMeMeFusionMePoint5R,2B8R,3B7R,2BMeMeMeMeFusionvs.bridgedpoints:theremustbeatle
2、astonecarbonCH2CH2(notintheringinquestion)betweenthecarboninquestionandanotherMeMecarbonintheringforittobeabridgedpoint.5R,4B6R,3B5R,4BMeMeMeMeMeMebacebCH2CH2CH2dcMeMeMe5R,4BMedMeeMeHMeaCH2CHMeH2MeMeMeCH2Menon-strategicgivesnon-strategicgives8-memberedring8-memberedringH---Oppolzerbutvia5-member
3、edringMemuchsimplerthanlongifolene!---CoreyandMcMurrydisconnection---SchultzdisconnectionSimultaneousorsequentialb/dbonddisconnection:---Brieger,Fallis(Diels-Alder);Johnson(cation-olefin).Simultaneousa/ebonddisconnection:---Schultz(indirectviavinylcyclopropanerearrangement).SynthesisHighlights1.
4、CoreySynthesisOOOOMeMeMeCH=PPh3MeOsO4,MeOHOH60%O96%O100%ORobinsonKetoneWittigRxnDi-OHOAnnulationOReactivitiesOStereoMeOOOMeOMeMeOMeLiClO4OOTsCl,PyO2NHClMeOOHOHPinacolOMeOHOTsRearrangement5%41-48%MeMeOOMeMeMeMeSMe0.95eq.OLAH;Ph3CLiMeNa-NH2NH2;OTEA,10-20%OCH3I,60%SHSHSRuO4OODesulfurization;HMeWolf
5、f-KishnerIntramolecularMeThermodynamicDiastereomericMichaelAdditionEnolateMeDerivatizationandMeReductionChromatographicMeResolutionMeMeMeMeLi,93%SOCl2,PyJACS1961,83,1251.OCH2JACS1964,86,478.MeMeCoreySynthesisOOOOLiClO4OMeoCaCO3,50COHMeOTsRCH3TsOORR'JACS1961,83,1251.TsOOOR'JACS1964,86,478.HHOPina
6、colRearrangement•LiClOusedforfreeLi+iontoacceleratesolvolyticlossofTsO-group.4•Migrationofunsaturatedalkylgroupobservedpreferentially.•TransantiperiplanararrangementCoreySynthesisOMeOEt3N,HO(CH2)2OHOOo225CMeH10-20%MeMeOOOJACS1961,83,1251.OJACS1964,86,478.BA5%5%IntramolecularMichaelAddition•Onlyc
7、isproductundergoesMichael.•Sideproductsincludetheretro-MichaelproductAandtheOH-additionandretro-aldolproductB.2.McMurrySynthesisOOHOOOMeMeLiMeMeMeMeH2,Pd/CMCPBAO85%OH2SO4DMSO-NaHO93%MeMeOOHcisHPeracidOHIntramolecularRobinson
