有机化学 ›› 2005, Vol. 25 ›› Issue (04): 347-354.    下一篇

综述与进展

仿生催化剂——Salen金属络合物催化不对称环氧化烯烃的基础

周智明*,李连友,徐巧,余从煊   

  1. (北京理工大学化工与环境学院 北京 100081)
  • 收稿日期:2003-12-11 修回日期:2004-09-10 发布日期:2005-03-30
  • 通讯作者: 周智明

Bionic Catalyst: Salen-metal Complex Catalyzed Asymmetric Epoxidation of the Olefins

ZHOU Zhi-Ming*,LI Lian-You,XU Qiao,YU Cong-Xuan   

  1. (School of Chemical Engineering & the Environment, Beijing Institute of Technology, Beijing 100081)
  • Received:2003-12-11 Revised:2004-09-10 Published:2005-03-30
  • Contact: ZHOU Zhi-Ming

Salen与卟啉、Salen金属络合物与卟啉铁的结构和性质相似, 因此可将Salen金属(Salen-M)络合物认为是仿生催化剂, 它们的仿生性突出表现在不对称催化反应中的高对映异构选择性. 重点介绍了Salen-M络合物催化环氧化烯烃的反应机理, 环氧化合物的对映选择性与Salen配位体中的取代基效应(以取代常数σp表示)之间呈线性关系. 另外, 对映异构选择性的高低还与催化剂配体和底物的结构以及反应条件有关.

关键词: 酶, Salen-M络合物, 对映异构选择性

The salen and porphyrin have the similar structures and properties, and salen-M and metalloporphyrin complexes have also the similarities. In this review, the salen-M complex was crowned as a bionic catalyst. It is believed that effective stereochemical communication between substrate and enzyme is essential for attaining high enantioselectivity in asymmetric reaction, and most of the successful salen-M catalysts also operate on this principle. According to these, salen-M complex catalyzed asymmetric epoxidation for olefins was discussed in detail, and the linear relationship between enantioselectivities and 5,5'-substituen effect on salen was developed. Moreover, enantioselectivities were still related to the structure of the salen-M complexes and substrates, as well as the reaction conditions.

Key words: salen-M complex, enzyme, enantioselectivity