醛的不對(duì)稱烯丙基化反應(yīng)及應(yīng)用研究.pdf

1、加夕善Z博士學(xué)位論文⑧王，8‘6‘27論文題目醛煎丕壁塹凌煎基垡基廛叢廛用盟窒作者姓名睦互熊指導(dǎo)教師盛邀壁耋邀隧查苤查邀學(xué)科(專業(yè))垡塋三堡叢墊盎所在學(xué)院鹽粒魚垡墨堂墮提交日期!Q!!生!屋AbstractThiswork，concentratedontheasymmetricallylationofaldehydescontrolledbydifferentchiralauxiliariespreparedfromrotational

2、puretartaricacid，canbedividedintothreepartsThefirstpartaimstOreviewthedevelopmentsofchimldrugsandasymmetricsynthesis，fromwhichderivedthepresentresearchtopicbackgroundsandworksSynthesisandapplicationsofallylationfromaldeh

3、ydesarethesecondpartofthethesisByoptimizingthereactionconditions，such船solvents，temperature，timeandchiralauxiliarieslikeNN1dmenzyltartamide，N，N’一Pdimethylphenyltartamide，N。N’odimethylphenyltartamide，N，N’Odichlorophenyltar

4、tamide，NN’a—dinaphyltartamide，N，N‘dicyclohexyltartamideandN，N’d毋henyltartamide，idealexperimenttalconditionsareobtainedaccordingtOHPLCmonitoring，aswellastheauxiliariesrecoveriesexperimentsStartingfrombenzaldehydeand3bromo

5、propaldehyde，N，N’一dmenzyltartamideisconsideredthebestauxiliaryinthisreactiortThehomoallylicalcoholproduct’(4R)4hydroxy6一bromo。1hexylene，canbeeasilysynthesizedinto(3R，5S)3hydroxy5iodomethyld。valerolactone，averyimportantin

6、termediateofAtorvastatininexcellentenantiomericexcess(941％ee)Inasimilarway，usingN，N’dlToenzyltartamideasauxiliary(S)2methyl)aUyl2chloro—phenylmethylazide，avitalintermediateofRepaglinide，canbepreparedviaasymmetricallylati

7、onofo—chlorobenzaldehydein877％eeTheauxiliarycanberecoveredinhighyield(引％)onlybyfilteringandrecrystallizationBesides，someotheraldehydeshavebeenchosentOtesttheenantioselectivityofN，Ndibenzyltartamide，incomparisonwithtwooth

8、erallylaboratesreagenBdevelopedpreviouslybyRoushandBrownrespectivelyTheresultsshowthat‰eofhomoallylicalcoholissuperiortOthatoftheformer，andapproachestheBrownreagentThethirdpartofthisthesisisreactivesimulmingcalculatiortI

9、nthissectionsomewellknownauxiliariesareselectedtOcomputeindens時(shí)functionaltheoryB3LYPonGaussian03，fromwhichtherelationshipbetweenreactbnactiveenergiesoftransitionstatesandenantiomericexcessofchiralproductshomoallylicalcoh