手性金属磷酸盐催化2-萘酚与亚胺不对称反应  

Chiral metal phosphate catalyzed asymmetric reaction of 2-naphthol and imine

作　　者：刘芮含 李红亮 LIU Ruihan;LI Hongliang(School of Pharmaceutical Science and Technology Tianjin Universit,Tianjin 300072,China)

机构地区：[1]天津大学药物科学与技术学院,天津300072

出　　处：《精细化工》2020年第9期1940-1944,共5页Fine Chemicals

基　　金：中国博士后科学基金资助项目(2018M641642)。

摘　　要：以2,6-二异丙基-4-金刚烷基苯取代的BINOL骨架磷酸镁盐作为催化剂,催化2-萘酚与N-(叔丁氧羰基)-苯甲醛亚胺(Ⅲa)的不对称反应。在常温、反应时间15h,甲苯作溶剂,催化剂用量5%(以底物的物质的量为基准,下同)的条件下,反应生成的叔丁基(2-羟基萘-1-基)(苯基)氨基甲酸甲酯(Ⅳa)达到97%的产率和90%的对映选择性。用NMR和HPLC对产物进行了表征。对反应条件进行了优化,确定了催化剂、反应时间、溶剂、反应温度等关键参数。该催化方法能使用少量的催化剂进行高效催化,且反应条件温和、经济高效、绿色环保。The asymmetric reaction of 2-naphthol and tert-butyl benzylidenecarbamate(Ⅲa) was carried out by using 2,6-(isopropyl)2-4-adamantyl-C6 H2 substituted BINOL skeleton magnesium phosphate as catalyst. Under the conditions of room temperature, reaction time 15 h, toluene as solvent, and dosage of catalyst 5%(based on the amount of substrate of substrate, the same below), tert-butyl(2-hydroxynaphth-1-yl)(phenyl) methylcarbamate(Ⅳa) in 97% yield was obtained with 90% enantioselectivity. The products were characterized by NMR and HPLC. The reaction conditions were optimized and the key parameters such as catalyst, reaction time, solvent, and reaction temperature were detetmined. A small amount of catalyst can efficiently catalyze the reaction. The reaction condition is mild. And the method is cost-effective and environmentally friendly.

关 键 词：手性磷酸催化剂 FRIEDEL-CRAFTS反应 不对称反应 催化方法 精细化工中间体 

分 类 号：O621.3[理学—有机化学]