酚氧基修饰的AlPS-PVPA固载手性Salen Mn(Ⅲ)催化剂的合成及催化烯烃不对称环氧化研究  

Synthesis of Chiral Salen Mn(Ⅲ) Complex Immobilized on Phenoxy-modified AlPS-PVPA as Catalysts for Epoxidation of Olefins

作　　者：王一帆[1] 范益梅 蹇君 潘雨民 赵亮[1] 敬雪平 周圣家 谌晓洪[1] 杜泉[1] 王玲[1] 吴小菊[4] 傅相锴[4] Wang Yifan Fan Yimei Jian Jun Pan Yumin Zhao Liang Jing Xueping Zhou Shengjia Chen Xiaohong Du Quana Wang Ling Wu Xiaojud Fu Xiangkai(School of Science, Xihua University, Chengdu 610039 School of Construction and Management Engineering, Xihua University, Chengdu 610039 School of Electrical and Electronic Information, Xihua University, Chengdu 610039 College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715)

机构地区：[1]西华大学理学院,成都610039 [2]西华大学建设与管理工程学院,成都610039 [3]西华大学电气与电子信息学院,成都610039 [4]西南大学化学化工学院,重庆400715

出　　处：《化学学报》2017年第7期715-722,共8页Acta Chimica Sinica

基　　金：西华大学研究生创新基金(No.ycjj2017101);四川省教育厅重点项目(No.14ZA0113)资助~~

摘　　要：以有机共聚物-无机杂化材料聚(苯乙烯-苯乙烯基膦酸)-磷酸铝(AlPS-PVPA)为载体,酚氧基为连接基团,轴向配位手性salen Mn(Ⅲ)制备了新型固载手性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,在相同的条件下,固载催化剂3a^3d在不加助催化剂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(ee%,99.2 vs.45.9;conv%,98.6 vs.64.6),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9次仍能保持较好的催化活性.Chiral epoxides are versatile intermediates that can be readily converted into a wide variety of enantiomerically pure compounds by means of region- and stereo-selective ring opening reactions. The asymmetric epoxidation of unfunctionalized olefins is an important approach for synthesizing optically active epoxides, and thus is widely used in the synthesis of fine chemicals, such as pharmaceuticals, agrochemicals and perfumes. Chiral salen Mn（Ⅲ） complexes have demonstrated activities and selectivities for the enantioselective epoxidation of unfimctionalized olefins under homogeneous conditions. Compared with the homogeneous asymmetric catalysts, the heterogeneous ones have the advantages of easy catalyst/product separation and simple catalyst recycling. And more and more interests have been focused on the studies of heterogenization of chiral complexes. New types of supported catalysts are obtained by anchoring chiral salen Mn（III） complex on a series of phenoxy-modified aluminium poly（styrene-phenylvinylphosphonate）-phosphate （A1PS-PVPA） in the text. All the prepared catalysts are characterized by FT-IR, UV-vis, XPS, SEM, TG and elemental analysis. The catalytic capabilities are investi- gated with m-CPBA as an oxidant and with indene and a-methylstyrene as substrates for asymmetric epoxidation of unfunc- tionalized olefins. The supported catalysts indicate superior catalytic activities in the asymmetric epoxidation of a-methylstyrene and indene with rn-CPBA as oxidative system, compared with the corresponding homogeneous catalyst （ee, 〉97% vs. 54% and 〉99% vs. 65%）. The steric properties of the linkages really play vital impacts on the configuration of the transition state for the asymmetric reactions. Contrary to most of the literatures reported, the results show that the hetero- geneous catalysts 3a-3d exhibit excellent catalytic activities, and their conversions and ee values increase remarkably in the absence of N-methylmorpholine N-oxide （NMO） under the same catalytic conditio

关 键 词：聚(苯乙烯-苯乙烯基膦酸)-磷酸铝 酚氧基修饰 Salen Mn(Ⅲ) 非功能化烯烃 不对称环氧化反应 

分 类 号：O621.251[理学—有机化学]