【作者】 温慧慧；

【导师】 王云普；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2007， 硕士

【摘要】 高分子手性催化剂具有分离简单,可循环使用等多相催化剂的优点,克服了昂贵的均相催化剂回收困难等缺点,符合绿色化学和可持续发展的需要。本论文的主要工作首先是对聚合物负载的手性催化剂的发展及在不对称催化反应中的应用进展作了综述;本文通过两种方法合成和表征了10种新的聚合物负载的手性催化剂并研究了它们在不对称双羟基化反应和不对称还原反应中的应用,主要由以下三章组成。第一章文献综述本章综述了金鸡纳碱类手性催化剂的发展、不对称催化及近年来聚合物负载金鸡纳生物碱催化剂在不对称双羟基化反应、不对称烷基化反应、潜手性酮的不对称还原反应及烯烃的不对称环氧化反应中的应用,并展望了聚合物负载手性催化剂的未来研究方向及应用前景。第二章聚丙烯酸负载手性季铵盐的合成与表征及其不对称催化性能研究本章分为两节,以辛可宁和对苯二甲酸双辛可宁酯为原料,首次合成了6种聚丙烯酸负载手性季铵盐相转移催化剂,采用红外光谱、元素分析、X-射线光电子能谱对所得的手性季铵盐的结构进行了表征;并将所得的手性季铵盐作为烯烃不对称双羟基化反应的催化剂,研究了所得手性季铵盐对不同的底物的催化性能,用HPLC等分析手段定量检测了产物的收率及其对映异构体选择性,比较了不同体系中产物的选择性、底物的转化率、并考察了反应时间、反应温度、催化剂和底物投料比和循环次数对催化性能的影响。结果表明,所合成的催化剂对AD反应有较好的催化效果。第三章聚-4-氨甲基苯乙烯负载金鸡纳碱金属络合物的合成与表征及其不对称催化性能研究本章分为两节,以辛可宁和奎宁及聚-4-氨甲基苯乙烯为原料,合成了4种聚-4-氨甲基苯乙烯负载金鸡纳碱络合物催化剂,并对它们的结构用元素分析、X-射线光电子能谱、TG/DTA等几种测试手段进行了表征;首次将所合成的手性高分子负载的金属络合物用于催化芳香酮不对称还原反应,详细研究了所得的手性高分子负载的金属络合物对不同底物的催化性能,用HPLC等分析手段定量检测了还原过程的底物转化率及其产物对映异构体选择性,并考察了反应时间、反应温度、催化剂和底物投料比、反应溶剂和循环次数对催化性能的影响。结果表明,所合成的催化剂性能稳定且有一定的催化效果。更多还原

【Abstract】 Polymer-supported chiral catalysts have many merits which are easily removed at the end of the reaction and can possibly be re-used and overcome these problems such as the high cost and difficulty in reusability of homogeneous catalysts. Adapt to the need of green chemical industry and sustainable development. In this paper, the application and development of polymer-supported chiral catalysts in asymmetric reaction were reviewed; kinds of new polymer-supported chiral catalysts were synthesized and characterized and the application of polymer-supported chiral catalysts in the asymmetric dihydroxylation reaction and the asymmetric reduction reaction of prochiral ketone was discussed. The thesis consists of three parts as follows.Part I : ReviewCinchona alkaloid catalysts, asymmetric catalyze, the application and recent development of polymer-supported cinchona alkaloid catalysts in asymmetric dihydroxylation reaction, the alkylation of active methylene group, asymmetric reduction reaction of prochiral ketone and asymmetric synthesis of chiral epoxides by catalyzing alkenes were reviewed. As a kind of newly catalysts, their prospect and the problems they faced were also discussed in this part.Part II: The synthesis and the characterizing of the PAA-supported chiral quaternary ammonium salts catalysts and the study on its catalytic propertiesThe part consists of two subsections. The PAA-supported chiral quaternary ammonium salts catalysts were synthesized by the stuff (cinchonine or BCIP). Their structures were characterized by means of FT-IR, elemental analysis, XPS; the chiral quaternary ammonium salts were first used as catalysts for the dihydroxylation of olefins. Their catalytic properties for the AD processes were investigated. The comparison of the products e.e., the conversion of the substrate among different AD processes was employed with determined by HPLC. The effects of the time, the temperature, the ratio of catalyst to substrate as well as the recycle times were also discussed. It is demonstrated that the chiral quaternary ammonium salts catalysts exhibit promising catalytic properties for the substrate.Part III: The synthesis and the characterizing of the macroporous aminomethyl resin-supported cinchona alkaloid complexes and the study on its catalytic propertiesThe part consists of two subsections. the macroporous aminomethyl resin -supported cinchona alkaloid complexes were synthesized by the stuff (cinchonine, quinine and macroporous aminomethyl resin). Their structures were characterized by means of elemental analysis, XPS, TG/DTA; the chiral polymer-supported complexes were first used as catalysts for the reduction of ketones. Their catalytic properties for the reduction processes were investigated. The comparison of the products e.e., the conversion of the substrate among different reduction processes was employed with determined by HPLC. The effects of the time, the temperature, the ratio of catalyst to substrate, reaction solvent as well as the recycle times were also discussed. It is demonstrated that the recovered catalyst can be reused without appreciable loss of activity.更多还原