手性磷酸硼催化的α-亚氨基酸酯的不对称还原  

Asymmetric Reduction ofα-Amino Acid Esters by Chiral Boron Phosphate

作　　者：孙卓鑫 司鑫鑫 曹阳[1,2] SUN Zhuo-xin;SI Xin-xin;CAO Yang(School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China;Jiangsu Key Laboratory of Marine Pharmaceutical Compound Screening, Jiangsu Ocean University, Lianyungang 222005, China)

机构地区：[1]天津大学药物科学与技术学院,天津300072 [2]江苏海洋大学江苏省海洋药物筛选重点实验室,江苏连云港222005

出　　处：《合成化学》2021年第12期1019-1025,共7页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(81703557)。

摘　　要：以H8-BINOL衍生的手性磷酸硼为催化剂,频哪醇硼烷为还原剂,实现了α-亚氨基酯的不对称还原。经过对反应条件的优化,确定了在0℃、反应36 h,催化剂用量5%(以底物的物质的量为基准,下同),3A分子筛添加量5 mg并以甲苯作为溶剂的条件下,生成的α-氨基酯可达到95%的产率和96%的对映选择性。底物及产物结构均经^(1)H NMR,^(13)C NMR和LC-MS(ESI)表征。该方法中生成的H8-BINOL衍生的手性磷酸硼是一种手性双功能催化剂,该催化剂催化的不对称反应具有条件温和、经济高效和绿色环保的特点。Chiral boron phosphate derived from H8-BINOL was used as catalyst,and pinacol borane was used as reducing agent for asymmetric hydrogenation ofα-imino ester to prepare optically pureα-amino ester.After optimizing the reaction conditions,the yields and enantioselectivities ofα-amino esters could be up to 95%and 96%respectively under the conditions of 0℃,reaction time 36 h,5%catalyst(based on the amount of substrate,the same below),5 mg 3Amolecular sieve in toluene.The structures of the substrates and products were characterized by ^(1)H NMR,^(13)C NMR and LC-MS(ESI).The H8-BINOL-derived chiral boron phosphate generated in this method is a kind of chiral bifunctional catalyst,and the asymmetric reaction catalyzed by this catalyst has the characteristics of mild conditions,economic efficiency,green and environmental protection.

关 键 词：手性磷酸 频哪醇硼烷 不对称氢化 α-氨基酯 手性双功能催化剂 

分 类 号：O621.3[理学—有机化学]