物理化学学报 >> 2010, Vol. 26 >> Issue (10): 2711-2718.doi: 10.3866/PKU.WHXB20101017

催化和表面结构 上一篇    下一篇

手性胺修饰的羟基磷灰石负载RuCl2(TPP)3催化不对称氢化苯乙酮

张定林1,2, 杨朝芬1, 孙亚萍1, 付海燕1, 李瑞祥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, 绿色化学与技术教育部重点实验室, 成都610064;
    2. 第三军医大学药学院化学教研室, 重庆400038
  • 收稿日期:2010-04-22 修回日期:2010-06-07 发布日期:2010-09-27
  • 通讯作者: 陈华 E-mail:scuhchen@163.com

Asymmetric Hydrogenation of Acetophenone Catalyzed by RuCl2(TPP)3 Supported on Hydroxyapatite Modified with Chiral Amine

ZHANG Ding-Lin1,2, YANG Chao-Fen1, SUN Ya-Ping1, FU Hai-Yan1, LI Rui-Xiang1, CHEN Hua1, LI Xian-Jun1   

  1. 1. Key Laboratory of Green Chemistry and Technology, Ministry of Education, Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China;
    2. Department of Chemistry, School of Pharmacy,The Third Military Medical University, Chongqing 400038, P. R. China
  • Received:2010-04-22 Revised:2010-06-07 Published:2010-09-27
  • Contact: CHEN Hua E-mail:scuhchen@163.com

摘要:

采用共沉淀法制备了手性胺(L-脯氨酸、D-脯氨酸、(1R,2R)-1,2 -二苯基乙二胺二磺酸钠((1R,2R)-DPENDS) 、(1S,2S)-1,2 -二苯基乙二胺二磺酸钠((1S,2S)-DPENDS)) 修饰的羟基磷灰石(HAP). 并采用傅里叶变换红外(FT-IR) 光谱, 扫描电子显微镜(SEM),X 射线衍射(XRD) 和比表面积测定(BET) 等仪器分析手段对其进行表征. 以手性胺修饰的羟基磷灰石做载体负载RuCl2(TPP)3 催化苯乙酮不对称加氢反应, 详细考察温度、压力、碱的浓度、手性胺负载量等条件对催化反应的影响. 在氢气压力为5.0 MPa 、30 oC条件下反应4 h, 苯乙酮的不对称加氢反应, 可获得99.9% 转化率和77.8% 对映选择性, 其结果优于对应的均相催化反应. 实验结果证明, 催化反应在载体表面完成, 催化剂通过简单离心分离可循环使用.

 

关键词: 手性胺, 羟基磷灰石, RuCl2(TPP)3, 苯乙酮, 多相不对称加氢

Abstract:

Chiral amine (L-proline,D-proline, (1R,2R)-1,2 -diphenyl -1,2 -ethylene diamine sulfonate disodium ((1R, 2R)-DPENDS) and (1S,2S)-1,2 -diphenyl -1,2 -ethylene diamine sulfonate disodium ((1S,2S)-DPENDS)) modified hydroxyapatite (HAP) were prepared and characterized by Fourier transform infrared (FT -IR) spectrometry, scanning electron microscopy (SEM),X-ray diffraction (XRD), and Brunauer -Emmett -Teller (BET) surface area analysis. RuCl2 (TPP)3was supported on(1R,2R)-DPENDS modified HAP for the asymmetric hydrogenation of acetophenone. A detailed investigation about the effects of temperature, amount of alkali,H2 pressure, and concentration of DPENDS modified HAP on the activity and enantioselectivity of acetophenone hydrogenation was undertaken. Under the optimum reaction conditions of 30 oC, p(H2)=5.0 MPa, reaction time of 4 h, the conversion and enantioselectivity reached 99.9% and 77.8% enantiomeric excess (ee), respectively. The results indicated that the asymmetric hydrogenation was accomplished on the surface of the chiral amine modified HAP. The immobilized catalyst was separated from the products by simple centrifugation and reused without adding any other reagents.

 

Key words: Chiral amine, Hydroxyapatite, RuCl2(TPP)3, Acetophenone, Heterogeneous asymmetrichydrogenation

MSC2000: 

  • O643