RuCl_2[P(C_6H_5)_3]_2-(R,R)-DPEN催化萘乙酮不对称加氢反应  

Asymmetric Hydrogenation of Acetonaphthone Catalyzed by RuCl_2P(C_6H_5)_3_2-(R,R)-DPEN

作　　者：陶明[1] 熊伟[1] 陈华[2] 李贤均[2] 

机构地区：[1]西昌学院生化系,四川西昌615022 [2]四川大学化学学院有机金属络合催化研究所,四川成都610064

出　　处：《催化学报》2006年第12期1107-1110,共4页

摘　　要：合成了(R,R)-1,2-二苯基乙二胺((R,R)-DPEN)、钌和三苯基膦的三元配合物RuCl2[P(C6H5)3]2-(R,R)-DPEN,并将其用于萘乙酮的不对称加氢反应.考察了碱/催化剂的摩尔比、反应温度和氢气压力等对催化活性和对映选择性的影响.结果表明,多种因素对反应的转化率和对映选择性均有影响.在萘乙酮∶(CH3)3COK∶催化剂摩尔比为50000∶450∶1,氢气压力为4MPa,反应温度为25℃的条件下,反应16h时,萘乙酮生成α-萘乙醇的产率和对映选择性分别达到了100%和83%.A novel ruthenium complex RuCl2 [ P （C6H5）3 ]2-（ R, R ）-DPEN （DPEN = 1,2-diphenylethylenediamine） was synthesized and characterized by ^1H and ^31p NMR. The ruthenium complex was applied to the asymmetric hydrogenation of acetonaphthone. The effects of reaction temperature, hydrogen pressure, and molar ratio of base to catalyst on the activity and enantioselectivity were investigated in an isopropanol solution of （CH3）3COK. The results showed that the increase in the temperature and pressure accelerated the reaction but slightly decreased the enantioselectivity for （S）-α-naphthylethanol. Under the conditions of acetonaphthone： （CH3）3COK： Ru = 50 000 ： 450 ： 1 （molar ratio）, 4 MPa, 25 ℃, and 16 h, 83 % ee and 100 % yield of α-naphthylethanol were achieved.

关 键 词：钌膦配合物 手性二胺 萘乙酮 不对称催化加氢 α-萘乙醇 对映选择性 

分 类 号：O643.32[理学—物理化学]