新型手性配體的合成及其作為配體催化劑在醛的不對稱烷基化和硅腈化反應(yīng)中的應(yīng)用.pdf

1、南開大學(xué)博士學(xué)位論文新型手性配體的合成及其作為配體催化劑在醛的不對稱烷基化和硅腈化反應(yīng)中的應(yīng)用姓名：楊卓鴻申請學(xué)位級別：博士專業(yè)：有機(jī)化學(xué)指導(dǎo)教師：唐除癡2001.4.1墮要奎堂重垂墮三墨莖二旦壁主蘭些堡苧SynthesisofNewChiralLigandsasCatalystsforAsymmetricAlkylationandSilylcyanationofAldehydesAbstractInthispaperthesynthe

2、sisofnewchiralligandsandtheirapplicationtoasymmetricalkylationandsilylcyanationofaldeh3，deswerediscussedFirstly，twentychiralreagentsweredesignedandsynthesizedfromⅨ一phenylethylamine，binaphthol，Dcamphor，andv(一)一ephedrine，r

3、espectivelyThestructuresofnewcompoundswerecharacterizedbyelementalanalyse，1HNMR，and”PNMRTheasymmetricalkylationofaldehydesWascarriedoutbyusingcatalystatogiveashigheeas571％Theeffectsoftheamountsofcatalyst，reactiontemperat

4、ure，andreactantonenantioselectivitywerealsoexaminedTheasymmetricsilylcyanationofaldehydesWasinvestigatedbyusingcatalystsh—jandqs，respectivelyTheeffectsofcatalystamounts，molarratiosofligandandTi(O—Pd)4，theadditionofisopro

5、pylalcohol，thereactiontemperature，andreactantsonenantioselectivitywerealsoexaminedSeveralcatalystspromotethedesiredreactionswithmoderatetoexcellentenantiomericexcessThemethodformeasuringofenantiomericexcesswasinvestigate

6、dItwasfoundthattheesterificationofo—methoxylhydrinappearedtoproceedwitllracemizationThereactionmechanismofasymmetricalkylationandsilylcyanationofaldehydeswerediscussedandapossiblemechanismwasproposedKeywords：chiralligand