苯氧基修饰的ZPS-PVPA轴向配位固载手性Salen Mn(Ⅲ)催化剂的合成及催化非功能化烯烃的不对称环氧化反应研究  

Study on the Synthesis of Chiral Salen Mn(Ⅲ) Immobilized onto Phenoxyl Linker Group Modified ZPS-PVPA by Axial Coordination and the Asymmetric Epoxidation of Unfunctionalized Olefins

作　　者：邹晓川[1,2] 傅相锴[1] 罗云飞[1] 

机构地区：[1]西南大学化学化工学院应用化学研究所重庆市应用化学重点实验室三峡库区生态环境教育部重点实验室,重庆400715 [2]重庆教育学院生物与化学工程系,重庆400067

出　　处：《化学学报》2011年第4期431-437,共7页Acta Chimica Sinica

基　　金：重庆市高校重点实验室建设基金(No.20500104)资助项目

摘　　要：制备了两种经不同链长苯氧基修饰的有机聚合物-无机杂化载体ZPS-PVPA轴向固载手性Salen Mn(III)催化剂(1a,1b),将其应用于非官能烯烃的多相不对称环氧化反应.详细比较了1a,1b在不同氧源下对非功能化烯烃的不对称环氧化反应结果,研究发现:在以间氯过氧苯甲酸为氧源体系中,非均相催化剂1a,1b在轴向添加剂的参与下,产率与对映选择性都相当低,令我们感到意外的是,在没有轴向添加剂的参与下,产率与对映选择性反而却大大提高,与已知固载型手性Salen Mn(III)体系相关文献报道矛盾.尤其对于α-甲基苯乙烯,产率从14.3%升到60.9%;而对映选择性从29.4%增加到73.7%,ee比相应的均相手性Salen Mn(III)增加了21.7%.相似的规律在苯乙烯和茚的环氧化中也同时被发现.有望为固载型手性Salen Mn(III)工业应用奠定基础.同时对取得的反应结果与烯烃进攻活性中间体的进攻取向进行了初步探讨.The catalytic activity and selectivity of catalysts 1a, 1b were explored for the asymmetric epoxidation of unfunctionalized olefins using rn-CPBA as an oxidant system. Interestingly, the immobilized chiral salen-Mn（Ⅲ） catalyst shows higher yields and chiral induction in the absence of NMO than that obtained in the presence of NMO. This stands in contrast to the literatures reported. Especially for the epoxidation of α-methylstyrene （yield%： from 14.3% to 60.9%; ee%： from 29.4% to 73.7%）, and the catalyst 1b shows more 21.7% ee values was observed than corresponding homogeneous catalyst, similar pattern was reported in the epoxidation of styrene and indene, which may overcome the last obstacle for the potential industry application of chiral Jacobsen＇s catalyst. And we also preliminary studied the attack-oriented to intermediates.

关 键 词：轴向配位固载 非功能化烯烃不对称环氧化 手性Jacobsen催化剂 苯氧基修饰 聚(苯乙烯基-苯乙烯膦酸)-磷酸氢锆 

分 类 号：O643.36[理学—物理化学]