有机化学 ›› 2013, Vol. 33 ›› Issue (07): 1369-1381.DOI: 10.6023/cjoc201304005 上一篇    下一篇

综述与进展

铑催化的烯烃不对称氢甲酰化反应研究进展

贾肖飞a,b, 王正b, 夏春谷a, 丁奎岭b   

  1. a 羰基合成与选择性氧化国家重点实验室中国科学院兰州化学物理研究所 兰州 730000;
    b 金属有机化学国家重点实验室中国科学院上海有机化学研究所 上海 200032
  • 收稿日期:2013-04-06 修回日期:2013-04-22 发布日期:2013-04-24
  • 通讯作者: 丁奎岭 E-mail:kding@mail.sioc.ac.cn
  • 基金资助:

    国家自然科学基金(Nos. 21172237, 21121062, 21032009)资助项目.

Recent Advances in Rh-Catalyzed Asymmetric Hydroformylation of Olefins

Jia Xiaofeia,b, Wang Zhengb, Xia Chungua, Ding Kuilingb   

  1. a State Key Laboratory of Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000;
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2013-04-06 Revised:2013-04-22 Published:2013-04-24
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21172237, 21121062, 21032009).

烯烃的氢甲酰化反应是工业上最重要的均相催化反应之一, 而通过烯烃的不对称氢甲酰化反应合成光学活性醛, 对于药物、农药、香料和天然产物合成方面具有重要的意义. 近年来, 由于铑与膦配体形成的络合物在催化烯烃的不对称氢甲酰化反应中具有反应活性高、选择性好等优点而引起广泛关注. 通过调控铑络合物中手性膦配体的电子与立体化学环境, 已经成为实现不对称氢甲酰化反应高活性和高选择性最主要的方法. 主要介绍了近期在铑催化的不对称氢甲酰化反应研究方面取得的进展, 重点介绍几类代表性的手性膦配体在此类反应中的应用.

关键词: 醛, 不对称催化, 手性膦配体, 氢甲酰化, 烯烃,

Hydroformylation is one of the most important processes of homogeneous catalysis in industry. Asymmetric hydroformylation (AHF) of prochiral alkenes provides an efficient way to the synthesis of optically active aldehydes, which are versatile chiral intermediates for pharmaceuticals, agrochemicals, and other fine chemicals. So far, most of methods reported were focused on the use of Rh(I)-based catalysts, by virtue of their high catalytic activity and excellent chemoselectivity for the aldehydes. A key issue in searching for efficient asymmetric hydroformylation catalysts is the development of new chiral ligands. A number of chiral phosphorus ligands have been successfully developed for Rh(I)-catalyzed AHF reactions. In this review, the recent advances in the development of chiral ligands for the Rh-catalyzed asymmetric hydroformylaion of olefins have been surveyed.

Key words: aldehyde, asymmetric catalysis, chiral phosphine ligand, hydroformylation, olefin, rhodium