物理化学学报 >> 2009, Vol. 25 >> Issue (10): 2039-2044.doi: 10.3866/PKU.WHXB20090935

研究论文 上一篇    下一篇

(1S,2S)-1,2-二苯基乙二胺修饰Ir/HAP催化苯乙酮及其衍生物的不对称加氢反应

张定林, 杨朝芬, 冯建, 付海燕, 陈华, 李瑞祥, 李贤均   

  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|第三军医大学药学院化学系, 重庆 400038
  • 收稿日期:2009-04-22 修回日期:2009-06-19 发布日期:2009-09-29
  • 通讯作者: 陈华 E-mail:scuhchen@163.com

Asymmetric Hydrogenations of Acetophenone and Its Derivatives over Ir/HAP Modified by (1S, 2S)-DPEN

ZHANG Ding-Lin, YANG Chao-Fen, FENG Jian, FU Hai-Yan, CHEN Hua, LI Rui-Xiang, LI Xian-Jun   

  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|Department of Chemistry, School of Pharmacy, Third Military Medical University, Chongqing 400038, P. R. China
  • Received:2009-04-22 Revised:2009-06-19 Published:2009-09-29
  • Contact: CHEN Hua E-mail:scuhchen@163.com

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摘要：

采用浸渍法在温和条件下制备了羟基磷灰石负载的铱催化剂(Ir/HAP), 并以X射线衍射(XRD), 透射电子显微镜(TEM), X射线光电子能谱(XPS), 比表面积测定(BET)以及附带能量散射X射线谱的扫描电子显微镜(SEM-EDS)等手段对载体和催化剂进行了表征. 以(1S,2S)-1,2-二苯基乙二胺((1S,2S)-DPEN)为手性修饰剂时, 该催化剂对苯乙酮及其衍生物不对称加氢反应表现出较高活性和对映选择性(ee). 在氢气压力为3.0 MPa、303 K条件下反应3 h, 苯乙酮及其衍生物的加氢转化率在94.7%以上, 其中生成2'-(三氟甲基)苯乙醇的对映选择性高达81.5%. 在不使用其它配体作稳定剂的情况下, 该结果比目前文献报道值高. 通过对比研究发现, 羟基磷灰石作为载体优于二氧化硅等其它无机载体. 催化剂通过简单离心分离可循环使用多次, 无明显的金属铱流失.

关键词: 羟基磷灰石, 铱, 苯乙酮, 不对称加氢, (1S,2S)-1,2-二苯基乙二胺

Abstract:

A novel catalyst was prepared for the first time by supporting iridium on porous hydroxyapatite (Ir/HAP). The catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy(SEM) equippedwithanenergydispersiveX-rayspectroscopy(EDS),X-rayphotoelectronspectroscopy(XPS), and Brunauer-Emmett-Teller (BET) surface area analysis. In the presence of (1S,2S)-1,2-diphenyl-1,2-ethylenediamine ((1S,2S)-DPEN), the catalytic properties of the catalyst were investigated by the asymmetric hydrogenation of aromatic ketones. Under optimum reaction conditions of temperature T=303 K, pressure p=3.0 MPa, and reaction time t=3 h, the conversion of aromatic alcohols that were produced from the hydrogenation of acetophenone and its derivatives reached 94.7%. The enantiomeric excess (ee) value for the 2'-(trifluoromethyl) phenethyl alcohol was 81.5%. Without using other ligands as stabilizers, the enantiomeric excess value was found to be higher than that reported in literature. As a catalyst carrier, hydroxyapatite is superior to SiO2 and other inorganic carriers. The catalyst is reusable with no sign of Ir leaching.

Key words: Hydroxyapatie, Iridium, Acetophenone, Asymmetric Hydrogenation, (1S,2S)-DPEN