物理化学学报 >> 2013, Vol. 29 >> Issue (07): 1572-1581.doi: 10.3866/PKU.WHXB201304243

催化和表面科学 上一篇    下一篇

金鸡纳碱衍生物修饰的负载铱催化剂催化芳香酮不对称加氢

蒋和雁1, 吴志峰1, 陈华2   

  1. 1 重庆工商大学药物化学与化学生物学研究中心 重庆工商大学环境与生物工程学院重庆高校催化理论与应用技术市级重点实验室 重庆 400067;
    2 四川大学化学学院有机金属络合催化研究所 绿色化学及技术教育部重点实验室 成都 610064
  • 收稿日期:2013-02-04 修回日期:2013-04-22 发布日期:2013-06-14
  • 通讯作者: 蒋和雁, 陈华 E-mail:scuhchen@163.com; orgjiang@163.com
  • 基金资助:

    国家自然科学基金(21201184); 重庆市科委自然科学基金计划(CSTC, 2011BA5025); 重庆工商大学科研启动基金(2010-56-14); 重庆市百名学术学科领军人才培养计划和重庆市科技创新团队(KJTD201020)资助项目

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by Cinchona-Modified Ir/SiO2

JIANG He-Yan1, WU Zhi-Feng1, CHEN Hua2   

  1. 1 Key Laboratory of Catalysis Science and Technology of Chongqing Education Commission, College of Environmental and Biological Engineering, Research Center of Pharmaceutical Chemistry and Chemical Biology, Chongqing Technology and Business University, Chongqing 400067;
    2 Key Laboratory of Green Chemistry and Technology, Ministry of Education, The Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064
  • Received:2013-02-04 Revised:2013-04-22 Published:2013-06-14
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21201184), Natural Science Foundation Project of Chongqing, China (CSTC, 2011BA5025), Research Fund of Chongqing Technology and Business University, China (2010-56-14), 100 Leading Scientists Promotion Project of Chongqing and Chongqing Innovative Research Team Development Program in University, China (KJTD201020).

摘要:

以金鸡纳碱衍生物作为手性修饰剂, 研究了三苯基膦稳定的Ir/SiO2催化剂催化芳香酮多相不对称加氢. 通过电感耦合等离子体原子发射发谱(ICP-AES)、高分辨透射电镜(HRTEM)、X 射线光电子能谱(XPS)、Brunauer-Emmett-Teller (BET)比表面积测试等固体表面分析手段对负载铱催化体系进行了表征; 利用红外(IR)光谱、固体核磁共振(NMR)等分析手段初步表征了负载铱多相催化体系中手性修饰剂-金属-稳定剂在载体上的相互作用; 利用“均相与多相催化体系的对比”、“催化剂稳定性实验”、“汞中毒实验”等方法阐明了手性修饰的负载铱催化体系是多相催化体系. 还考察了稳定剂种类、修饰剂种类、金属负载量、溶剂、碱添加剂种类等因素对不对称加氢反应的影响. 结果表明, 金鸡纳碱衍生物对Ir/SiO2催化剂具有较好的修饰作用, 在优化反应条件下苯乙酮及其衍生物加氢反应的对映选择性为52%-96%, 4-乙酰基吡啶、2-乙酰基噻吩及2-乙酰基呋喃加氢反应的对映选择性可分别达到74%、75%及63%.

关键词: 铱, 金鸡纳碱, 芳香酮, 不对称加氢, 负载催化剂

Abstract:

The asymmetric hydrogenation of aromatic ketones catalyzed by cinchona- and triphenylphosphine (tpp)-modified Ir/SiO2 was studied. The heterogeneous enantioselective hydrogenation of heterocyclic ketones using a supported iridium catalyst was also investigated. Different analytical techniques, including inductively coupled plasma-atomic emission spectroscopy (ICP-AES), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), the Brunauer- Emmett-Teller (BET) method, infrared (IR) spectroscopy, 31P solid state nuclear magnetic resonance (NMR) spectroscopy, homogeneous- heterogeneous comparison experiment, conventional filtering test, and mercury poisoning experiment, were used to characterize the catalytic system. HRTEM, XPS, and the BET method clearly characterized the catalytic system. IR and 31P solid state NMR spectra provided useful information about the interactions between modifier, metal, and stabilizer. The homogeneous-heterogeneous comparison experiment, conventional filtering test, and mercury poisoning experiment clearly showed the differences between supported, and homogeneous catalysts. In addition, the effects of different stabilizers, modifiers, iridium content, solvents, and base additives on the asymmetric hydrogenation of aromatic ketones were investigated in detail. The results showed that cinchona alkaloids positively modified the Ir/ SiO2 catalyst. Under the optimum conditions, the hydrogenation enantioselectivities of acetophenone and its derivatives were 52%-96%. The enantioselectivities of the hydrogenation products of 4-acetopyridine, 2-acetothiophene, and 2-acetofuran reached 74%, 75%, and 63%, respectively.

Key words: Iridium, Cinchona alkaloid, Aromatic ketone, Asymmetric hydrogenation, Supported catalyst

MSC2000: 

  • O643