催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (7): 601-606.

• 研究论文 • 上一篇    下一篇

糖衍生的手性Salen-Mn(Ⅲ)配合物的合成及其在不对称环氧化中的应用

赵姗姗,赵继全,何乐芹,李娜,赵东敏   

  1. 河北工业大学化工学院, 天津 300130
  • 收稿日期:2007-07-25 出版日期:2007-07-25 发布日期:2011-07-25

Preparation of Sugar-Based Chiral Salen-Mn(Ⅲ) Complex and Its Application in Asymmetric Epoxidation

ZHAO Shanshan, ZHAO Jiquan*, HE Leqin, LI Na, ZHAO Dongmin   

  1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
  • Received:2007-07-25 Online:2007-07-25 Published:2011-07-25

PDF

712

被引次数

14

摘要： 利用1,2:5,6-二氧-异丙叉基-3-氧-亚甲基-[5-(3-叔丁基-2-羟基苯甲醛)]-α-D-呋喃葡萄糖与(1S, 2S)-(-)-1,2-二苯基乙二胺缩合生成新型手性Salen配体,再与Mn3+配位制得糖衍生的手性Salen-Mn(Ⅲ)配合物. 利用核磁共振波谱、傅里叶变换红外光谱、紫外-可见光谱和元素分析方法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,考察了该配合物催化烯烃不对称环氧化反应的性能. 结果表明,在配体羟基的对位引入手性糖基对催化效果有一定的影响. 并且以m-CPBA为氧化剂考察了催化剂在离子液体[bmim]PF6中苯乙烯环氧化反应的循环使用性能. 催化剂在使用四次后,对映体过量值仍能达到51%.

关键词: 不对称环氧化, Salen-Mn(Ⅲ)配合物, 葡萄糖衍生物, 二苯基乙二胺, 离子液体

Abstract: A novel chiral salen ligand was synthesized through the reaction of1,2:5,6-di-O-isopropylidene-3-O-methylene-[5-(3-tert-butyl-2-hydroxybenzaldehyde)]-α-D-glucofuranose with (1S,2S)-(-)-1,2-diphenylethylenediamine. The sugar-based chiral salen-Mn(Ⅲ) complex was prepared from this ligand. The ligand and complex were characterized by nuclear magnetic resonance, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and elemental analysis. The complex was then used as a catalyst for the asymmetric epoxidation of alkenes using NaClO and m-chloroperoxybenzoic acid as the oxidants. The results showed that the chiral sugar moiety that was incorporated into C5(5′) of the ligand had certain effect on enantioselectivity. Furthermore, the recycle ability of the catalyst was studied in the epoxidation of styrene with m-chloroperoxybenzoic acid as terminal oxidant in the presence of the ionic liquid [bmim]PF6. The enantiomeric excess of the epoxides was still 51% even after the catalyst was used three times.

Key words: asymmetric epoxidation, salen-Mn(Ⅲ) complex, glucose derivative, diphenylethylenediamine, ionic liquid