复杂分子的合成（上海有机所）-03AB

《复杂分子的合成（上海有机所）-03AB》由会员上传分享，免费在线阅读，更多相关内容在行业资料-天天文库。

1、第四部分：反合成分析一、基本概念1©2004YZJ-SIOC反合成分析¢Retrosynthetic(orantithetic)analysisisaproblem-solvingtechniquefortransformingthestructureofasynthetictarget(TGT)moleculetoasequenceofprogressivelysimplerstructuresalongapathwaywhichultimatelyleadstosimpleorcommerciallyavai

2、lablestartingmaterialsforachemicalsynthesis.¢Thetransformationofamoleculetoasyntheticprecursorisaccomplishedbyapplicationofatransform,theexactreverseofasyntheticreaction,toatargetstructure.Corey&Cheng,TheLogicofChemicalSynthesis,1989.2©2004YZJ-SIOC断裂转化和反合成子(T

3、ransformsandRetrons)HHHHHCarbo-Diels-AlderTransformHHHHHHHHHMeMeCOOMeCOOMeMeCOOMeCOOMeCOOMeMeOOCHH3©2004YZJ-SIOC练习MeO2COHMeO2CSNHNPhNSMeO2COHHOHH4©2004YZJ-SIOC断裂转化（1）TGTRetronTransformPrecursor(s)MePhO(E)-EnolatePhCHO+MeCOtCOtBu2Bu2HOCCAldolOHPhPhPhPhOO+Micha

4、elOOCCCOOCO2MeMeO2CRobinsonAnnulation+OOOOOOOMannichRxnNMe2+CH2O+Me2NNCCMeNCHOODouble+MeCHO+ONCCMannichRxnCHOO5©2004YZJ-SIOC断裂转化（2）TGTRetronTransformPrecursor(s)OHOHOOrganometallic+Et-MetHOOMeClaisenMe+RearrangementOXMeOOHHFisherIndole+NH2NNNOHHHOOOxy-lactoni

5、zationOOOofOlefinHOHOHO6©2004YZJ-SIOC可以考虑或利用的结构因素¢分子骨架：连接与重排¢官能团：相互转化¢立体化学：翻转或转移7©2004YZJ-SIOC简化断裂分析的官能团策略¢官能团转换（FGI)¢官能团移位（FGT)¢重排（Rearrangement)¢官能团添加（FGA)¢官能团消除（FGR)8©2004YZJ-SIOCFunctionalGroupInterchange(FGI)H2NMeOMeOConia(Oxo-ene)FGICHOHHCyclizationHHHO

6、NO2FGIMeNO2MeMePhPhOPhONefRxnO9©2004YZJ-SIOCFunctionalGroupTransposition(FGT)OTMSOTMSOHHMeFGTMeMeMeMeMeHHMeOMeOMeO10©2004YZJ-SIOCRearrangementHOxy-CopeClCNOHO+OHPinacolOORearrangementOHHOO11©2004YZJ-SIOCFunctionalGroupAddition(FGA)Part1OOOOOFGAOMeMeOOMeHOOCHH

7、HHHHPhPhPhPhPhPhPhHHOFGAOCOHClHClClCl12©2004YZJ-SIOCFunctionalGroupAddition(FGA)Part2NH2NHII2FGAIIIIOFGASSSRR13©2004YZJ-SIOCFunctionalGroupAddition(FGA)Part3FGAOHOR'R'R'RRRSO2PhSO2PhROROROMeFGAOHOHOOOHOPhMeMeMeROOOPhMeMe14©2004YZJ-SIOCFunctionalGroupRemoval(F

8、GR)1TGTRetronTransformPrecursor(s)OMeOMeAromaticBrominationBrBrMeMeAllylicOxidationOofCH2toC=OOMeMeAllylicOxidationby1DO,withC=Cg2TransportantionHOOHHOOOMeOROMeo-Metallation(RLi)andCarbox