催化学报

催化学报 ›› 2006, Vol. 27 ›› Issue (8): 683-689.

• 研究论文 • 上一篇    下一篇

手性低聚环状salen-Mn(Ⅲ)配合物的合成及其催化烯烃不对称环氧化反应的性能

何乐芹,赵继全,张雅然,赵东敏,赵姗姗   

  1. 河北工业大学化工学院, 天津 300130
  • 收稿日期:2006-08-25 出版日期:2006-08-25 发布日期:2010-09-28

Preparation of Chiral Oligomeric Cyclic salen-Mn(Ⅲ) Complex and Its Catalytic Performance for Asymmetric Epoxidation of Olefin

HE Leqin, ZHAO Jiquan*, ZHANG Yaran, ZHAO Dongmin, ZHAO Shanshan   

  1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
  • Received:2006-08-25 Online:2006-08-25 Published:2010-09-28

PDF

893

被引次数

28

摘要： 合成了新型二水杨醛衍生物,将其与(1R,2R)-环己二胺缩合制备出手性低聚环状salen配体,该配体再与Mn3+配位制得手性低聚环状salen-Mn(Ⅲ)配合物. 利用核磁共振光谱、傅里叶变换红外光谱、紫外可见光谱、凝胶渗透色谱和元素分析等手段对配体和配合物进行了表征. 分别以NaClO和间氯过氧苯甲酸(m-CPBA)为氧化剂,考察了该salen-Mn(Ⅲ)配合物催化烯烃不对称环氧化反应的性能. 结果表明,该配合物对顺-β-甲基苯乙烯的不对称环氧化反应具有很好的催化性能,产物选择性达96%, ee值达78%. 以顺-β-甲基苯乙烯为底物,m-CPBA为氧化剂,考察了该配合物催化剂的循环使用性能.

关键词: 不对称环氧化, 非官能化烯烃, 低聚salen-Mn(Ⅲ)配合物, 电子效应, 轴向配体

Abstract: A novel chiral oligomeric cyclic salen ligand was synthesized by the reaction of a novel dialdehyde with (1R,2R)-1,2-diaminocyclohexane. From this ligand, the chiral oligomeric cyclic salen-Mn(Ⅲ) complex was prepared. The ligand and complex were characterized by nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy, UV-Vis spectroscopy, gel permeation chromatography, and elemental analysis. The complex was used as a catalyst for the asymmetric epoxidation of olefin using NaClO and m-chloroperoxybenzoic acid as the oxidants, respectively. In the asymmetric epoxidation of cis-β-methylstyrene, the selectivity and enantiometric excess for the epoxides reached 96% and 78%, respectively. The recyclability of the catalyst was also studied.

Key words: asymmetric epoxidation, non-functional olefin, oligomeric salen-Mn(Ⅲ) complex, electronic effect, axial ligand