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有机化学
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有机化学 ›› 2006, Vol. 26 ›› Issue (04): 559-562. 上一篇    下一篇

研究简报

RuCl2(BISBI)[(R,R)-DPEN]催化苯乙酮不对称加氢反应研究

陶明1,2，陈丽1，熊伟1,2，袁茂林1，陈华*,1，李贤均1   

  1. (1四川大学化学学院有机金属络合催化研究所 成都 610064)
    (2西昌学院生化系 西昌 615022)
  • 收稿日期:2005-04-28 修回日期:2005-10-31 发布日期:2006-03-31
  • 通讯作者: 陈华

Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl2(BISBI)(R,R-DPEN)

TAO Ming1,2,CHEN Li1,XIONG Wei1,2,YUAN Mao-Lin1
CHEN Hua*,1,LI Xian-Jun1   

  1. (1 Institute of Homogeneous Catalysis, College of Chemistry, Sichuan Univer-sity, Chengdu 610064)
    (2 Department of Biology and Chemistry, Xichang College, Xichang 615022)
  • Received:2005-04-28 Revised:2005-10-31 Published:2006-03-31
  • Contact: CHEN Hua

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报道了配合物RuCl2(BISBI)[(R,R)-DPEN] [BISBI＝2,2'-二(二苯膦亚甲基)-1,1'-联苯, DPEN＝1,2-二苯基乙二胺]的合成和表征, 并研究了其在苯乙酮不对称加氢反应中的催化性能. 考察了底物/催化剂物质的量比、碱浓度、反应温度和氢气压力等对催化活性和对映选择性的影响, 在苯乙酮/KOH/催化剂的物质的量比为30000∶250∶1, 氢气压力为2 MPa, 反应温度为35 ℃时, 苯乙酮的转化率和生成α-苯乙醇的对映选择性分别达到了100%和65% ee.

关键词: 不对称催化加氢, 苯乙酮, 手性二胺, 钌-膦配合物

The synthesis of ruthenium complex, RuCl2(BISBI)(R,R-DPEN) (1) [BISBI: 2,2'-bis(diphenylphosphinomethyl)-1,1'-biphenyl, DPEN: 1,2-diphenylethylenediamine] and the application to the asymmetric hydrogenation of acetophenone are reported. The effect of reaction temperature, hydrogen pressure, base concentration and molar ratio of substrate to catalyst on the activity and enantioselectivity of ruthenium catalyzed asymmetric hydrogenation of acetophenone was investigated in the iso-propanol solution of KOH. The results showed that the increase of temperature and pressure accelerated the reaction rate but just decreased slightly the enantioselectivity. Under the optimum conditions of ketone∶KOH∶Ru＝30000∶250∶1 (molar ratio), 2 MPa, 35 ℃, 6 h, the hydrogenation of acetophenone gave S-1-phenylethanol with 65% ee and 100% of yield.

Key words: acetophenone, ruthenium complex, chiral diamine, asymmetric hydrogenation