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  

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

作　　者：何乐芹[1] 赵继全[1] 张雅然[1] 赵东敏[1] 赵姗姗[1] 

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《催化学报》2006年第8期683-689,共7页

基　　金：国家自然科学基金资助项目(20376017)

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.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, Fouriertransform 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 NaCIO 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.

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 

分 类 号：O641.4[理学—物理化学] O643.32[理学—化学]