【作者】 张皓；

【导师】 张雅文；

【作者基本信息】 苏州大学 ， 有机化学， 2005， 硕士

【摘要】 一、手性氨基醇在不对称Reformatsky 反应中的应用从易得的天然(L)-脯氨酸出发,设计并合成了两类四种手性氨基醇催化剂(1a~1d), 用于催化不对称Reformatsky 反应,产率48%-73%,e.e.17.4%-74.9%,考察了催化剂用量、反应温度、底物取代基的电子效应等因素对反应的影响。 二、氨基酸促进的四烯丙基锡与羰基化合物加成反应研究以天冬氨酸为促进试剂,通过烯丙化反应直接制得系列含有三氟甲基的高烯丙醇,产率51.5%-92.6%。研究了底物取代基的电子效应,立体结构等因素对这一反应的影响。以易得的天然(L)-脯氨酸和(L)-天冬氨酸为原料, 合成两类三种氨基酸衍生物(A,B,C),并以三种氨基酸衍生物为手性促进试剂研究了四烯丙基锡与芳香醛的不对称烯丙化反应,产率73%-93%,e.e.0%-27 %。产物的绝对构型与文献报道的相反。此外,讨论了底物取代基的电子效应等因素对反应的影响。更多还原

【Abstract】 1. Asymmetric Reformatsky reactions catalyzed by chiral aminoalcohols Four novel chiral aminoalcohols(1a~1d) were prepared from (L)-proline and applied to the Asymmetric Refomatsky reactions. Various β-hydroxyesters were obtained in mild yields (48%-73%) and moderate ee’s(17.3%-74.9). The influences of the amount of the catalysts,the temperature and the electronic effect of the substrates were discussed. 2. Allylation of carbonyl compounds promoted by derivatives of aminoacids The allylation of several trifluoromethylketones with tetraallyltin promoted by L-aspartic acid was investigated. The relationship between the substrates structure and the yield was studied. Three chiral aminoacid derivatives,which were synthesized from L-proline and L-aspartic acid, were applied to the Asymmetric Allylation of aldehydes. Various homoallylicalcohols were obtained in high yields (73%-93%) and mild ee’s(0%-27.2%)更多还原