《手性合成英》PPT课件

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1、EliasJ.Corey－－Autobiography1928borninMethuen，Massachusetts1944enteredM.I.T.参与合成青霉素1950completeddoctoralworkjoinedUniversityofIllinois1956becameProfessorofChemistry1959workinHarvard1957年EliasJ.Corey提出了他的想法：TheLogicofChemicalSynthesisretrosyntheticanalysis逆合成法

2、Thelogicofchemicalsynthesis简单的原料复杂的分子transformsynthesis反合成分析法retrosyntheticanalysisretrosyntheticanalysisRetrosynthetictree树根－－目标分子树枝－－原料BestChoice?位置控制保护基活化基桥连因子Tobuild"left-orrighthanded"moleculesHerbertC.BrownUSAPurdueUniversityWestLafayette,IN,USA1912-G

3、eorgWittigFederalRepublicofGermanyUniversityofHeidelbergHeidelberg,Germany1897-1987TheNobelPrizeinChemistry1979Laureates:HerbertC.BrownGeorgWittig"fortheirdevelopmentoftheuseofboron-andphosphorus-containingcompounds,respectively,intoimportantreagentsinorgan

4、icsynthesis"BoroncompoundsHerbertCBrownsodiumboro-hydride(硼氢化钠)--thereagentofchoiceforreductionofcarbonylcompoundsOrganoboranes(B2H6)(themostversatilereagentsevercreatedinorganicchemistry)canbeusedforreductions,rearrangementsandadditionsandhaveopeneduparange

5、ofnewpossibilitiesforlinkingcarbonatomstoeachother.还原重排加成Wittigreactionorganicphosphoruscompoundwithaformaldoublebond(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,theproduc

6、tbeinganolefin(烯烃)。这是我们熟悉的Wittig试剂，用于双键化合物的制备Acarbonylcompound(羰基化合物)organicphosphoruscompoundwithaformaldoublebondbetweenphosphorusandcarbonolefin(烯烃)Fig.1.Formationofadiradical被削弱的C-C键demetalization有机金属锂化合物diradicalFormationandcharacterizationofcompound9zi

7、ncdustdistillation.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Reversalofpolarity(umpolung)极性逆转Mechanismofformationofo-lithiobiphenylProofoftheintermediateoccurrenceofdehydrobenzeneinthereactionof14C-labeledchlorobenzenewithpotassiumamideinliquidammoniaFig.8.Pr

8、oofoftheexistenceofdehydrobenzenethroughtheformationof10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：经证实，苯炔中间体存在的时间为：20milliseconds.Thermaldecompositionreactionsusedtodeterminethelifetim