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高等学校化学研究 ›› 2004, Vol. 20 ›› Issue (2): 180-184.

• Articles • 上一篇    下一篇

New Chiral Metal Cluster Systems for Catalytic Asymmetric Syntheses of Chiral Alcohols

LI Yan-yun1, CHEN Jian-shan1, YANG Chuan-bo1, DONG Zhen-rong1, LI Bao-zhu1, ZHANG Hui1, GAO Jing-xing1, TAKAO Ikariya2   

  1. 1. Department of Chemistry, Institute of Physical Chemistry, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, P. R. China;
    2. Graduate School of Science and Engineering, Tokyo Institute of technology & CREST, 2-12-1 O-okayama, Meguro-ku, Tokyo152-8552, Japan
  • 收稿日期:2003-12-05 出版日期:2004-04-24 发布日期:2011-08-06
  • 基金资助:

    Supported by the National Natural Science Foundation of China (No.20073034,20373056,20171037), Fujian Province and Technology Commission (No.2002F016) and Xiamen Science and Technology Commission(No.3502Z20021044).

New Chiral Metal Cluster Systems for Catalytic Asymmetric Syntheses of Chiral Alcohols

LI Yan-yun1, CHEN Jian-shan1, YANG Chuan-bo1, DONG Zhen-rong1, LI Bao-zhu1, ZHANG Hui1, GAO Jing-xing1, TAKAO Ikariya2   

  1. 1. Department of Chemistry, Institute of Physical Chemistry, State Key Laboratory of Physical Chemistry of Solid Surface, Xiamen University, Xiamen 361005, P. R. China;
    2. Graduate School of Science and Engineering, Tokyo Institute of technology & CREST, 2-12-1 O-okayama, Meguro-ku, Tokyo152-8552, Japan
  • Received:2003-12-05 Online:2004-04-24 Published:2011-08-06
  • Supported by:

    Supported by the National Natural Science Foundation of China (No.20073034,20373056,20171037), Fujian Province and Technology Commission (No.2002F016) and Xiamen Science and Technology Commission(No.3502Z20021044).

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摘要： The efficient chiral Ru3(CO)12 systems were prepared in situ from Ru3(CO)12 and various chiral diiminoor diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu3(CO)11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru3 framework.

关键词: Chiral cluster systems, Asymmetric transfer hydrogenation, Aromatic ketones

Abstract: The efficient chiral Ru3(CO)12 systems were prepared in situ from Ru3(CO)12 and various chiral diiminoor diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu3(CO)11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru3 framework.

Key words: Chiral cluster systems, Asymmetric transfer hydrogenation, Aromatic ketones