手性氮氧自由基修饰聚吡咯对仲醇的电氧化动力学拆分及机理

项目名称： 手性氮氧自由基修饰聚吡咯对仲醇的电氧化动力学拆分及机理

项目编号： No.21206147

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 化学工程及工业化学

项目作者： 李美超

作者单位： 浙江工业大学

项目金额： 26万元

中文摘要： 外消旋仲醇的动力学拆分是获得手性仲醇的重要方法之一，而采用电化学氧化法实现仲醇的动力学拆分是一符合绿色化学要求的重要课题。针对目前电氧化动力学拆分过程中使用的手性氮氧自由基催化剂存在底物适应性和结构刚性较差、催化剂难以回收等问题，本项目提出以含吡咯侧链的结构可调且立体效应较强的新型手性2-氮杂金刚烷氮氧自由基(AZADO)衍生物为单体，原位电聚合制备手性AZADO衍生物修饰的聚吡咯（AZADO-PPy）用于仲醇的动力学拆分。项目中重点探讨不同结构AZADO-PPy对仲醇的电氧化动力学拆分效率，明确不同结构手性AZADO衍生物与底物仲醇的匹配关系；采用电化学原位红外光谱和原位拉曼光谱等技术，阐明AZADO-PPy对仲醇的电氧化动力学拆分机理。本项目对于实现仲醇的动力学拆分具有明显的优势和创新性，通过系统研究，为AZADO-PPy催化的仲醇电氧化动力学拆分的工业化应用提供科学指导和理论依据。

中文关键词： 电氧化；动力学拆分；氮氧自由基；苯甲醇；聚吡咯

英文摘要： The kinetic resolution of racemic secondary alcohols is an important method to obtain optically active secondary alcohols. Kinetic resolution of secondary alcohols via electrooxidation is an important subject which fulfills the principles of green chemistry. There are several drawbacks in the electrooxidative kinetic resolution of secondary alcohols using chiral nitroxyl radicals as catalysts at present, such as low substrate tolerance, low rigidity of structure, and low recyclability. In this proposed project, chiral AZADO derivatives-modified polypyrrole (AZADO-PPy) will be prepared by electrochemical polymerization of novel chiral AZADO derivatives which contain a pyrrole side chain and possess adjustable structure and strong steric effects. Effect of the AZADO-PPy structures on efficiency of electrooxidative kinetic resolution of secondary alcohols will be investigated. Matching relationship between the AZADO-PPy structures and secondary alcohol substrates will be ascertained. In situ FTIR, in situ Raman and other technologies will be used to clarify the mechanism of electrooxidative kinetic resolution of secondary alcohols with AZADO-PPy. There are obvious superiority and innovation to achieved kinetic resolution of secondary alcohols in this project. It can be expected that the successful research will pro

英文关键词： electrochemical oxidation；kinetic resolution；nitroxyl radical；benzyl alcohol；polypyrrole