仿生催化剂——Salen金属络合物催化不对称环氧化烯烃的基础  

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

作　　者：周智明[1] 李连友[1] 徐巧[1] 余从煊[1] 

机构地区：[1]北京理工大学化工与环境学院,北京100081

出　　处：《有机化学》2005年第4期347-354,共8页Chinese Journal of Organic Chemistry

摘　　要：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.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.

关 键 词：SALEN 金属络合物 不对称环氧化 仿生 烯烃 不对称催化反应 基础 对映异构 催化环氧化 取代基效应 对映选择性 环氧化合物 催化剂配体 反应机理 线性关系 反应条件 卟啉铁 配位体 结构 相似 常数 

分 类 号：O643.32[理学—物理化学]