高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (9): 1615.

• 研究快报 • 上一篇    下一篇

芳香酮的高效对映选择性转移氢化

潘恩德, 李岩云, 董振荣, 陈建珊, 李宝珠, 章慧, 高景星   

  1. 厦门大学化学系固体表面物理化学国家重点实验室, 厦门 361005
  • 收稿日期:2003-02-10 出版日期:2003-09-24 发布日期:2003-09-24
  • 通讯作者: 商景星(1942年出生),男,教授,博士生导师,从事有机金属化学、均相催化与不对称催化合成研究.E-mail:jxgao@xmu.edu.cn E-mail:jxgao@xmu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20073034,20171037);福建省科技厅重大科技项目基金(批准号:2002F016);厦门市科技局重大科技项目基金(批准号:3502Z20021044)

Highly Enantioselective Transfer Hydrogenation of Aromatic Ketones

PAN En-De, LI Yan-Yun, DONG Zhen-Rong, CHEN Jian-Shan, LI Bao-Zhu, ZHANG Hui, GAO Jing-Xing   

  1. State Key Laboratory for Physical Chemistry of Solid Surface, Department of Chemistry, Xiamen University, Xiamen 361005, China
  • Received:2003-02-10 Online:2003-09-24 Published:2003-09-24

摘要: 手性芳香醇在制药工业上有重要的应用,因而利用芳香酮的对映选择性氢化制备相应的手性醇已引起人们极大关注.近10年来,用手性金属配合物为催化剂,利用种种有机物作氢源,实现芳香酮的不对称氢转移氢化取得了很大进展.但这些反应过程的催化活性仍然较低,底物酮与催化剂.

关键词: 手性胺膦配体, 铱配合物, 芳香酮, 对映选择性氢化

Abstract: Enantioselective reduction of prochiral ketones with 2-propanol or formic acid catalyzed by chiral metal complexes has been developed as a synthetic method complementary to asymmetric hydrogenation in the past decade. However, these processes are necessary to be improved for practical use in organic synthesis because of low catalytic activity and insufficient enantioselectivity. In this paper, we wish to report an excellent catalytic system generated in situ from iridium complex IrCl(Ph3P)3and chiral tetradentate di-aminodiphosphine ligand for asymmetric transfer hydrogenation of various aromatic ketones. For isobuty-rophenone transfer hydrogenation, the corresponding optically active alcohol was obtained in 93% yield and with up to 99% e. e. after 5h at 28℃. Propiophenone was a better substrate with respect to catalytic activity and enantioselectivity in the presence of base as a co-catalyst. The conversion of propiophenone reached 95. 8% and the turnover number as high as 3193h-1. These results will provide a useful index for further designing practical chiral catalytic systems.

Key words: Chiral aminophosphine ligand, Iridium complex, Aromatic ketones, Enantioselective transfer hydrogenation

中图分类号: 

TrendMD: