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1、实例讲解实例讲解VIVI---Gelsemine的全合成GelsemineGelsemine:AThought:AThought--ProvokingProvokingTargetforTotalSynthesisTargetforTotalSynthesis---LinandDanishefsky.Angew.Chem.2003,42,36.18O1H21.Gelsemine,IsolatedfromNgelsemiumsempervirens,wasfirst122067notedintheliteraturein1870.
2、8X14321N52.DegradativeandspectroscopicO410Me16datawereavailablebyConroyin171959.1:X=H,HGelsemine2:X=O(Alsoanaturalproduct)3.X-raybyLovelletal.in1959.4.TheattractiontogelsemineasaTodate,seventotaltargetintotalsynthesishasbeensynthesesof1havedrivenbyitsfascinating3-Dbe
3、enreported.architecture.NewChemistryLearntbyPracticeNewChemistryLearntbyPracticeAssemblingvarioussubsectionsAssemblingvarioussubsectionsofthemoleculeofthemolecule18OH12N1.Bicyclo[3.2.1]octaneskeleton.12206782.TheC20stereogeniccenter.X143215NO4103.TheC7stereogeniccent
4、er16Me17anchoringthespiro-oxindole.1:X=H,HGelsemine2:X=O(Alsoanaturalproduct)4.Thepyrrolidinemoiety.5.TheveryhinderedTHPringontheconcavefaceofthemolecule.I.StrategiesfortheAssemblyofI.StrategiesfortheAssemblyofBicycloBicyclo[3.2.1][3.2.1]--octaneSkeletonoctaneSkeleto
5、n18OH12N1220678143215NO41016Me17Gelsemine1.1.TheformationofC5TheformationofC5--C6BondC6Bond------TheFleming,TheFleming,OvermanOverman,andJohnsonApproaches,andJohnsonApproaches18O1H2LowselectivityofDAreaction,butaquickN122067accesstothebicyclounitwithrequired814321fun
6、ctionalityandstereochemistry.5NO41016Me17Fleming,etal.Tetrahedron1988,44,3931.cat.pyrogallol,PhHOTHP0oCtortOTHPOHpNO-CHCOHON2643243%+39%exo81%over5steps85%+O2NEtO2CHNCO2MeOAcCO2MeMgBr2Et2OBrOOHPhH-THFOH678%HOOHO5EtO2CHNEtOCHNEtO2CHNOAcOAc2OAc18OHTheidealgeometrytodel
7、ivertricyclicproductwith1N212thequaternaryC20carbonatomandthe20678143pyrrolidinemoietyembedded(12steps-16%yield).215NO41016Overman,etal.Tetra.Lett.1988,29,3781.Me17SeO2OSiiPr3AlCl3,DCMiPh3P=CH2OSiiProOSiPr33-78C,76-83%62%-90%64%over3steps+CO2MeCO2MeCO2MeKH,18-C-6;OSi
8、iPr3ClCH2CN;OHClCO2Me;OKOKTBAF,90%KOH,81%[3,3]NNHCHCNN5NH2216HOOHO2067MeO2CN3215TFANNBr2X=H67%MeO2C16HEBrbaseX=BrXBrH18O1H2NPhotoin
