手性合成英文

EliasJ.Corey

－－Autobiography

1928 borninMethuen，Massachusetts1944 enteredM.I.T. 参与合成青霉素1950 completeddoctoralworkjoinedUniversityofIllinois1956 becameProfessorofChemistry1959workinHarvard

11957年EliasJ.Corey提出了他的想法：TheLogicofChemicalSynthesis

retrosyntheticanalysis

逆合成法2Thelogicofchemicalsynthesis简单的原料

复杂的分子

transformsynthesis反合成分析法retrosyntheticanalysis

3retrosyntheticanalysis4Retrosynthetictree

树根－－目标分子树枝－－原料BestChoice?5位置控制

保护基活化基桥连因子67Tobuild"left-orrighthanded"molecules

8910HerbertC.Brown

USAPurdueUniversity

WestLafayette,IN,USA1912-11GeorgWittig

FederalRepublicofGermanyUniversityofHeidelberg

Heidelberg,Germany1897-198712TheNobelPrizeinChemistry1979Laureates:HerbertC.Brown

GeorgWittig

"fortheirdevelopmentoftheuseofboron-andphosphorus-containingcompounds,respectively,intoimportantreagentsinorganicsynthesis"13

BoroncompoundsHerbertCBrownsodiumboro-hydride(硼氢化钠)--thereagentofchoiceforreductionofcarbonylcompoundsOrganoboranes(B2H6)(themostversatilereagentsevercreatedinorganicchemistry)14canbeusedforreductions,rearrangementsandadditionsandhaveopeneduparangeofnewpossibilitiesforlinkingcarbonatomstoeachother.还原重排加成15Wittigreactionorganicphosphoruscompoundwithaformaldoublebond(含双键的有机磷化合物，双键在P和C之间)betweenphosphorusandcarbonreactwithacarbonylcompound(羰基化合物).Theoxygenofthecarbonylcompoundisexchangedforcarbon,theproductbeinganolefin(烯烃)。16

这是我们熟悉的Wittig试剂，用于双键化合物的制备Acarbonyl

compound(羰基化合物)organicphosphoruscompoundwithaformaldoublebondbetweenphosphorusandcarbonolefin(烯烃)17Fig.1.Formationofadiradical被削弱的C-C键18demetalization

有机金属锂化合物

diradical19Formationandcharacterizationofcompound9zincdustdistillation.20芳基质子作为取代基的不稳定性惊人发现：umpolung规则或极性逆转规则F的特异性21Reversalofpolarity(umpolung)极性逆转22Mechanismofformationofo-lithiobiphenyl23Proofoftheintermediateoccurrenceofdehydrobenzeneinthereactionof14C-labeledchlorobenzenewithpotassiumamideinliquidammonia24Fig.8.Proofoftheexistenceofdehydrobenzenethroughtheformationof10苯炔中间体存在的证实：在反应过程中加入二烯体呋喃，分离出产物10aDiels-Alderaddition：25经证实，苯炔中间体存在的时间为：20milliseconds.

Thermaldecompositionreactionsusedtodeterminethelifetimeofdehydrobenzeneinthegasphase26四烷基铵盐上的碳上的氢是否也有不稳定性？通过：氯化四甲基铵甲基锂

五甲基氮

失败！27FormationofNylides28ylide29FormationofP-ylides30N-ylide(氮叶立德)ThesemipolarnatureoftheN-CbondItsabilitytoaddtobenzophenone（二苯甲酮）31P-ylide（磷叶立德）triphenylphosphinemethylenetriphenylphosphineoxide1，1-diphenylethylene32

Fig.13.Stepsinthereactionoftriphenylphosphinemethylenewithbenzophenone四元环过度态33应用：vitaminA的合成

34硼也可以作为

tetracoordinatecentralatom35参考文献E.J.Corey,X.-M.Cheng:TheLogicofChemicalSynthesis,Wiley–Interscience,1989.E.J.Corey,A.K.Long,S.D.Rubenstein:Computer-AssistedAnalysisinOrganicSynthesis,Science,Vol228,1985,pp408-418.TheRoyalSwedishAcademyofSciences,InformationabouttheNobelPrizeinChemistry1990(pressrelease).

36FurtherreadingG.WittigandM.Rieber,ibid.562,187(1949).G.WittigandKClauss,ibid.577,26(1952);ibid.578,136(1952).G.WittigandK.Torssell,ActaChem.Stand.7,1293(1953).H.Pommer,Angew.Chem.89,437(1977).R.W.Hoffmann,Dehy