物理化学学报 >> 2010, Vol. 26 >> Issue (03): 675-678.doi: 10.3866/PKU.WHXB20100225

催化和表面结构 上一篇    下一篇

RuCl2[(S)-P-Phos]-[(S)-DAIPEN]催化芳香酮的不对称加氢反应

姜和, 王金波, 熊伟, 贾云, 秦瑞香, 刘德蓉, 陈华   

  1. 重庆科技学院化学化工学院, 重庆 401331; 四川大学化学学院, 绿色化学及技术教育部重点实验室, 成都 610064
  • 收稿日期:2009-09-04 修回日期:2009-10-26 发布日期:2010-03-03
  • 通讯作者: 王金波, 陈华 E-mail:scuhchen@163.com; wjb76@163.com

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by RuCl2[(S)-P-Phos]-[(S)-DAIPEN]

JIANG He, WANG Jin-Bo, XIONG Wei, JIA Yun, QIN Rui-Xiang, LIU De-Rong, CHEN Hua   

  1. College of Chemistry &Chemical Engineering, Chongqing University of Science and Technology, Chongqing 401331, P. R. China; Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China
  • Received:2009-09-04 Revised:2009-10-26 Published:2010-03-03
  • Contact: WANG Jin-Bo, CHEN Hua E-mail:scuhchen@163.com; wjb76@163.com

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摘要：

研究了钌-双膦-二胺配合物催化剂RuCl2[(S)-P-Phos]-[(S)-DAIPEN] [P-Phos: 2,2',6,6'-四甲氧基-4,4'-双(二苯基膦基)-3,3'-二吡啶, DAIPEN: 1,1-二(4-甲氧苯基)-2-异丙基-1,2-乙二胺]催化芳香酮不对称加氢反应的性能, 考察了不同的碱、叔丁醇钾浓度、反应溶剂、底物/催化剂摩尔比等因素对反应活性和对映选择性的影响. 在苯乙酮、叔丁醇钾、催化剂的摩尔比为1000:20:1, 氢气压力为2 MPa, 反应温度为30 ℃时, 苯乙酮的转化率和α-苯乙醇的对映选择性(ee)分别达到了100%和88.5%, 2'-溴苯乙醇的ee 值可达97.1%.

关键词: 不对称加氢, 钌膦配合物, 手性二胺, 芳香酮

Abstract:

A ruthenium phosphine diamine complex RuCl2[(S)-P-Phos]-[(S)-DAIPEN] [P-Phos: 2,2',6,6'-tetramethoxy-4,4'-bis(diphenylphosphino)-3,3'-bipyridine, DAIPEN: 1,1'-di(4-anisyl)-2-iopropyl-1,2-ethylenediamine] for the asymmetric hydrogenation of aromatic ketones has been studied. The influences of different bases , (CH3)3COK concentration, organic solvent, and molar ratio of substrate to catalyst on activity and enantioselectivity were investigated. Under the following optimum conditions: n(ketone):n(KOH):n(catalyst)=1000:20:1, pH2=2 MPa and T=30 ℃, the conversion of acetophenone and the enantioselectivity (ee) of S-1-phenylethanol was 100% and 88.5%, respectively. Additionally, the ee value of 2'-bromophenyl ethanol was 97.1%.

Key words: Asymmetric hydrogenation, Ruthenium-phosphine complex, Chiral diamine, Aromatic ketones

MSC2000: 

  • O641