Ru-(S)-BINAP/γ-Al_2O_3催化剂上苯乙酮及其衍生物的多相不对称加氢反应  

Heterogeneous Asymmetric Hydrogenation of Acetophenone and Its Derivatives over Ru-(S)-BINAP/γ-Al_2O_3

作　　者：黄艳轶[1] 马红霞[1] 熊伟[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,四川成都610064

出　　处：《催化学报》2004年第12期962-966,共5页

摘　　要：在温和条件下制备了Ru (S) BINAP/γ Al2 O3 催化剂 ,考察了其催化苯乙酮及其衍生物不对称加氢的活性 .在KOH 异丙醇溶液中 ,在c(KOH) =0 0 4mol/L ,氢气压力 5MPa和 10℃条件下 ,(1S ,2S) DPEN手性修饰剂修饰的Ru (S) BINAP/γ Al2 O3 催化剂具有较高的活性和对映选择性 ,反应 2 8h后苯乙酮的转化率可达 10 0 % ,(R) 苯乙醇的ee值可达 75 0 % .The enantioselective hydrogenation of acetophenone and its derivatives over Ru-(S)-BINAP/γ-Al 2O 3 catalyst using (1S,2S)-1,2-diphenylethylenediamine ((1S,2S)-DPEN) as chiral modifier was investigated. The effect of DPEN, concentration of KOH in i-PrOH, temperature, hydrogen pressure and reaction time on the asymmetric hydrogenation of acetophenone was discussed. (1S,2S)-DPEN played a key role in the chiral inducement and accelerated the asymmetric hydrogenation of acetophenone and its derivatives. Under the optimum conditions of concentration of KOH in i-PrOH of 0 04 mol/L, H 2 pressure of 5 0 MPa, temperature of 10 ℃ and reaction time of 28 h, the conversion of acetophenone and ee value of (R)-phenylethanol reached 100% and 75 0%, respectively. The Ru-(S)-BINAP/γ-Al 2O 3 catalyst could also be used in the asymmetric hydrogenation of acetophenone derivatives such as 2′-fluoroacetophenone, 2′-chloroacetophenone and 2′-bromoacetophenone, but ee values of their products were lower than that of α-phenylethanol produced from acetophenone hydrogenation.

关 键 词：苯乙酮 钌 手性配体 手性修饰剂 不对称加氢 苯乙醇 

分 类 号：O643[理学—物理化学]