基于壳聚糖结构的手性相转移催化剂设计合成及在不对称催化中应用

项目名称： 基于壳聚糖结构的手性相转移催化剂设计合成及在不对称催化中应用

项目编号： No.21302071

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 华明清

作者单位： 江苏大学

项目金额： 25万元

中文摘要： 作为自然界年合成量巨大的甲壳素的衍生物，壳聚糖用途广泛，但作为一个天然手性分子，其手性催化价值并未能得到充分的开发使用。现阶段，壳聚糖在不对称反应中的应用主要体现在负载金属及小分子手性催化剂。 本项目着眼于拓展壳聚糖手性应用范围，将其与手性联萘骨架结构相结合，合成出含多中心结构的手性季铵盐类相转移催化剂，并将其应用于二苯酮亚胺甘氨酸叔丁酯的不对称烷基化反应、烯酮的不对称环氧化反应和不对称Michael加成反应中，以研究多中心结构相转移催化剂在不对称催化中应用前景。同时通过向有机小分子催化剂中引入天然手性分子以达到优化催化剂之目标，并有望简化高效手性催化剂合成步骤，降低其合成成本，为有机小分子催化剂应用于实际生产提供新的支持。本项目的成功实施不仅能提高壳聚糖的附加经济价值，还具有较高学术意义。

中文关键词： 壳聚糖；手性相转移催化剂；不对称催化；二氟甲基化；

英文摘要： As a derivative of chitin which is huge synthesized by biology annually, chitosan is used widely, but as a natural chiral molecules, the value of chitosan in asymmetric catalysis has not been fully developed. Nowadays, the application of chitosan in asymmetric reactions is mainly reflected in the supported metal and organocatalyst chiral catalyst. This project mainly aims at expand the application scope of chitosan in asymmetric synthesis. Herein we plan to synthesize new chiral quaternary ammonium salts as phase-transfer catalysts (PTC) based on chitosan and chiral binaphthol with the structure of the multi-center, and use new PTC in the asymmetric alkylation reaction of N-(diphenylmethylene)glycine tert-butyl ester and asymmetric epoxidation addition and Michael reaction of ketene. Though the introduced in organocatalyst natural chiral molecular, hope to obtain the optimized catalyst in asymmetric catalysis and expect to simplify synthesis step of the efficient chiral catalyst while reducing the cost of synthesis and giving new support for organocatalyst used in the industry production. The successful implementation of the project, not only raises the chitosan additional economic value, but also has a high academic significance.

英文关键词： chitosan；chiral phase-transfer catalysts；asymmetric catalysis；difluoromethylation；