新型烷氧基修饰的手性SalenMn(Ⅲ)固载催化剂的合成及其在非功能化烯烃不对称环氧化反应中的应用  

Synthesis and Application of New Alkoxyl-Modified Immobilized Chiral Salen Mn(Ⅲ) Complexes in Asymmetric Epoxidation of Unfuntionalized Olefins

作　　者：王长炜[1,2] 傅相锴[1,2,3] 黄静[1,2] 

机构地区：[1]西南大学化学化工学院应用化学研究所,重庆400715 [2]重庆市应用化学市级重点实验室,重庆400715 [3]三峡库区生态环境教育部重点实验室,重庆400715

出　　处：《化学学报》2011年第14期1681-1687,共7页Acta Chimica Sinica

基　　金：国家科技部科技型中小企业技术创新基金(No.09C26215112399);国家人力资源和社会保障部留学人员回国创业启动支持计划(No.人社厅发2009(143)号)

摘　　要：合成了一系列以有机聚合物-无机杂化材料聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆(ZPS-PVPA)为载体,烷氧基为连接基团的新型固载手性Salen Mn(III)催化剂,并运用FT-IR,UV-vis,XPS,SEM,TG,元素分析等手段对其进行了表征.以m-CPBA为氧化剂,茚和α-甲基苯乙烯为底物,考察了催化剂对非功能化烯烃不对称环氧化反应的催化性能.结果表明,在相同的催化反应条件下,固载手性Salen Mn(III)催化剂3a～3f在不加轴向配体N-甲基吗啉氮氧化物(NMO)时显示出了优良的催化活性,其转化率和ee值均比添加了轴向配体NMO时有很大的提高,这种现象与大多数文献报道相反.此外,催化剂容易分离,且回收使用10次仍能保持较好的催化活性.New types of supported catalysts were obtained by anchoring chiral salen Mn（III） complex on a series of alkoxyl-modified zirconium poly（styrene-phenylvinyl phosphonate）-phosphate（ZPS-PVPA） in the text.All the prepared catalysts were characterized by FT-IR,UV-vis,XPS,SEM,TG and elemental analysis.The catalytic capabilities were investigated with m-CPBA as an oxidant and with indene and α-methylstyrene as substrates for asymmetric epoxidation of unfunctionalized olefins.Contrary to most of the literatures reported,the results showed that the heterogeneous catalysts 3a～3f exhibited excellent cata-lytic activities,and their conversions and ee values increased remarkably in the absent of N-methyl-morpholine N-oxide（NMO） under the same catalytic conditions.Futhermore,these catalysts were easily separated and reused ten times without significant loss of activities.

关 键 词：聚(苯乙烯-苯乙烯基膦酸)-磷酸氢锆 烷氧基修饰 SalenMn(III) 非功能化烯烃 不对称环氧化反应 

分 类 号：O643.36[理学—物理化学]