光催化芳基胺化在不对称去对称化中的应用

光催化芳基胺化是合成芳香胺类化合物的前沿策略之一，具有反应条件温和、无需过渡金属等优点。由于胺化过程不能直接在芳香环上产生手性中心，因此将光催化芳基胺化反应应用到不对称催化领域存在着巨大的挑战。我们预实验发现，可以通过去对称化的策略实现芳基胺化反应的手性诱导和转移。基于此，我们提出将“光催化芳基胺化”和“不对称去对称化”结合起来的设计理念，利用手性布朗斯特酸催化体系，分别以光催化C-H活化和亲核芳基取代两种胺化策略实现二苯甲基类化合物、联苯类化合物的不对称去对称化反应和动力学拆分反应，合成一系列含有芳香胺基团的手性分子。本项目发展的光催化不对称芳基胺化策略，将会推动芳基胺化反应在不对称催化领域的应用和发展，同时也为手性芳香胺类化合物提供一条新的合成途径。

Photocatalytic arylamination is one of the leading synthesis strategies for aromatic amines, which has the advantages of mild conditions and transition metals free. However, arylamination cannot generate chiral centers at the reaction sites, and how to apply aryl amination reactions to the field of asymmetric catalysis has always been a great challenge. Our preliminary experiments show that the chiral induction and transfer of aryl amination can be achieved through the strategy of desymmetrization. Therefore, we proposed the design concept of combining "photocatalytic aryl amination" with "enantioselective desymmetrization", using chiral Brønsted acid catalysts to realize the enantioselective desymmetrization reaction and kinetic separation reaction of diphenyl methyl compounds and biphenyl compounds by photocatalytic C-H activation and nucleophilic aryl substitution, respectively. The photocatalytic asymmetric aryl amination strategy developed in this project will promote the application and development of aryl amination reactions in the field of asymmetric catalysis, and also provide a new synthesis pathway for chiral aromatic amines.