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
收稿日期: 2017-01-02
网络出版日期: 2017-04-25
基金资助
项目受西华大学研究生创新基金（No.ycjj2017101）和四川省教育厅重点项目（No.14ZA0113）资助.
Synthesis of Chiral Salen Mn (III) Complex Immobilized on Phenoxy-modified AlPS-PVPA as Catalysts for Epoxidation of Olefins
Received date: 2017-01-02
Online published: 2017-04-25
Supported by
Project supported by the Innovation Fund of Postgraduate,Xihua University (No.ycjj2017101) and the key research fund of Sichuan Provincial Department of Education (No.14ZA0113).
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.
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
王一帆 , 范益梅 , 蹇君 , 潘雨民 , 赵亮 , 敬雪平 , 周圣家 , 谌晓洪 , 杜泉 , 王玲 , 吴小菊 , 傅相锴 . 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[J]. 化学学报, 2017 , 75(7) : 715 -722 . DOI: 10.6023/A17010002
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 unfunctionalized 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 (AlPS-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 investigated with m-CPBA as an oxidant and with indene and α-methylstyrene as substrates for asymmetric epoxidation of unfunctionalized olefins.The supported catalysts indicate superior catalytic activities in the asymmetric epoxidation of α-methylstyrene and indene with m-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 heterogeneous 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 conditions.The structures of the immobilized cat-alysts similar to the N-oxide ligand act as axial ligands leading to the unusual phenomenon.Simultaneously,additives are generally regarded as axial ligands on the transition metal catalyst,which make for activating the catalyst either toward oxidation or toward reactivity with the olefin.Thus,there is a steric hindrance when the N-oxide ligand is added and the optimal geometric configuration of the reactive intermediate salen Mn (V)=O was altered.It is steric hindrance that makes olefins approaching salen Mn (V)=O difficult and lower ee values are obtained.Furthermore,these catalysts are easily separated and are relatively stable and reused nine times without significant loss of activities.
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