氮相邻sp3C-H键不对称官能团化新策略及其应用研究

项目名称： 氮相邻sp3C-H键不对称官能团化新策略及其应用研究

项目编号： No.21302130

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： 冯高峰

作者单位： 绍兴文理学院

项目金额： 25万元

中文摘要： sp3 C-H 键不对称官能团化和有机小分子催化是当前有机合成前沿的两大研究热点。不对称氧化交叉脱氢偶联虽可实现氮相邻sp3 C-H 键的不对称官能团化，但该方法通常以叔胺为底物,以手性配体金属络合物为手性诱导且对映选择性不理想。该领域有待进一步研究。本项目拟在手性磷酸的催化和不对称诱导下，以非手性仲胺为原料，研究对其通过"原位氧化--不对称亲核加成"、"原位氧化--不对称环加成"和"原位氧化--不对称多组分反应"来实现仲胺氮相邻sp3 C-H 键高对映选择性地官能团化，并以此来合成结构多样的手性胺。本项目将有机小分子催化和sp3 C-H 键活化有机结合，用手性磷酸来活化原位氧化生成的亚胺并诱导后续不对称反应，是一种新颖的实现仲胺氮相邻sp3 C-H 键不对称官能团化的策略。项目既拓展了sp3 C-H 键不对称官能团化的策略，又拓宽了手性胺合成的方法和底物来源，具有重要学术意义和应用价值

中文关键词： sp3 C-H 活化；原位氧化；亚胺有机催化；可见光催化；异构化

英文摘要： Asymmetric functionalization of sp3 C-H bond and organocatalysis are two hot area in synthetic frontier. Althought asymmetric functionalization of sp3 C-H bond adjacent to nitrogen could be achieved through asymmetric oxidative cross-dehydrogenative coupling, tertiary amines and chiral metal complexes are commonly employed and the enantioselectivity is unsatisfied. Therefore, this erea needs further exploration. Employing achiral second amines as starting materials and chiral phosphoric acids as catalysts,this project focuses on establishing highly enantioselective asymmetric functionalization of sp3 C-H bond adjacent to the nitrogen of second amines for synthesizing chiral amines with structural diversity through strategies of "in-situ oxidation - asymmetric nucleophilic addition", "in-situ oxidation - asymmetric cycloaddition", and "in-situ oxidation - asymmetric multicomponent reaction".It is a new strategy to realize asymmetric functionalization of sp3 C-H bond adjacent to the nitrogen of second amines.Organocatalysis and sp3 C-H bond activation are combined together and chiral phosphoric acid is used to activate imine generated through in-situ oxiation and to control sebsequent asymmetric reactions. This project will not only broaden the strategy on asymmetric functionalization of sp3 C-H bond, but also wid

英文关键词： sp3 C-H activation；in-situ oxidation；imines organocatalysis；visible light catalysis；isomerization