摘要
以二苯基乙二胺为原料,分别与水杨醛、3,5-二叔丁基水杨醛、3,5-二甲氧基水杨醛反应合成了3种Salen配体,并与醋酸锌组成Salen-Zn络合物催化体系,考察其对芳香酮的不对称硅氢化反应的催化性能。结果表明,叔丁基Salen-Zn络合物催化体系的催化性能最优;以苯乙酮为模板底物,确定不对称硅氢化反应的最佳条件如下:(EtO)3SiH为还原剂、THF为溶剂、反应温度为30℃、反应时间为24 h,产物苯乙醇的收率为94%、ee值为98%。底物的拓展研究表明,Salen-Zn络合物催化体系对含不同官能团的芳香酮均具有良好的催化性能。该方法提供了一种高反应活性和高对映选择性合成手性芳香醇的途径,为手性药物的不对称合成以及活性中间体的开发提供了新思路。
Firstly,we synthesized three kinds of Salen ligands from diphenylethylenediamine with salicylaldehyde,3,5-di-tert-butylsalicylaldehyde,and 3,5-dimethoxy-salicylaldehyde,respectively.Then,we obtained Salen-Zn complex catalyst system by the Salen ligands with zinc acetate.Moreover,we investigated its catalytic performance to the asymmetric hydrosilylation of aromatic ketones.The results show that the tert-butyl Salen-Zn complex catalyst system has the best catalytic performance.Taking acetophenone as a model substrate,the optimum conditions for asymmetric hydrosilylation can be determined as follows:(EtO)3SiH is adopted as reducing agent,THF is adopted as solvent,the reaction temperature is 30℃,and the reaction time is 24 h.Under above conditions,the yield of phenylethanol can reach 94%,and ee value can reach 98%.The extended study of substrate shows that the Salen-Zn complex catalyst system has good catalytic performance for aromatic ketones containing different functional groups.This method provides a highly reactive and enantioselective way to synthesize chiral aromatic alcohols,and provides a new idea for the asymmetric synthesis of chiral drugs and the development of active intermediates.
作者
盛余豪
张朵朵
陈雅婷
葛燕丽
冯菊红
胡学雷
SHENG Yuhao;ZHANG Duoduo;CHEN Yating;GE Yanli;FENG Juhong;HU Xuelei(Key Laboratory of Green Chemical Process of Ministry of Education,School of Chemical Engineering and Pharmacy,Wuhan Institute of Technology,Wuhan 430074,China)
出处
《化学与生物工程》
CAS
2023年第5期49-52,56,共5页
Chemistry & Bioengineering
基金
湖北省自然科学基金重点项目(2011CDA048)。
关键词
手性催化剂
不对称硅氢化反应
手性芳香醇
芳香酮
chiral catalyst
asymmetric hydrosilylation
chiral aromatic alcohol
aromatic ketone
