水/有机两相体系中钌膦配合物催化苯乙酮及其衍生物的不对称加氢反应  

Asymmetric Hydrogenation of Acetophenone and Its Derivatives Catalyzed by Ruthenium Phosphine Complexes in Organic/Aqueous Biphase Catalytic System

作　　者：熊伟[1] 杨朝芬[1] 袁茂林[1] 陈华[1] 李贤均[1] 

机构地区：[1]四川大学化学学院有机金属络合催化研究所绿色化学与技术教育部重点实验室

出　　处：《催化学报》2005年第12期1093-1098,共6页

基　　金：国家自然科学基金资助项目(20272037)

摘　　要：将手性二胺(1S,2S)-1,2-二苯基乙二胺二磺酸钠((1S,2S)-DPENDS)修饰的钌膦配合物用于催化水/有机两相体系中苯乙酮的不对称加氢.结果表明,(1S,2S)-DPENDS和KOH的浓度对反应有很大影响,二者的协同作用使配合物的催化活性和产物的对映选择性大大提高.对温度、压力、底物/钌的摩尔比和膦配体/钌摩尔比等反应条件进行优化后,以[RuCl2-(TPPTS)2]2为催化剂前体催化苯乙酮不对称加氢时,产物的ee值可达66.4%,催化剂经过简单的相分离即可循环使用.The catalytic performance of ruthenium phosphine complex [ RuCl2 （TPPTS）2 ]2 （TPPTS： trisodium salt of tri （ rn -sulfophenyl） phosphine） using （ 1 S, 2 S）- 1,2-diphenyl-1, 2-ethylene diamine sulfonate disodium （ （1 S, 2 S）-DPENDS） as chiral modifier for the asymmetric hydrogenation of aeetophenone and its derivatives in an organic/aqueous biphase catalytic system was investigated. The concentration of （S, S）-DPENDS and/or KOH could strongly influence the catalytic performance of the ruthenium complex catalyst. The synergistic effect between （1 S, 2 S ）-DPENDS and KOH could significantly accelerate the reaction rate and enhance the enantioselectivity for （R）-phenylethanol. An ee value of 66.4 % was obtained under the optimized conditions. The products could be conveniently separated from the reaction system by decantation, and both the ruthenium com- plex catalyst and （1 S ,2S）-DPENDS were left in the aqueous phase and could be used repeatedly.

关 键 词：钌膦配合物 苯乙酮 两相体系 不对称加氢 对映选择性 苯乙醇 

分 类 号：O643.32[理学—物理化学]