可见光催化剂与有机分子协同作用下的不对称SP3 C-H活化反应研究

利用可见光催化协同手性诱导的不对称催化反应不仅为太阳能的有效利用提供了新途径，也为手性物质的合成提供了新方法和手段。. 本项目拟设计系列富电子的有机配体，与廉价易得的铜、铁等过渡金属形成配合物，获得稳定性好、激发态寿命长和氧化还原电位高的新型可见光催化剂。通过与手性有机分子（如手性胺、硫脲类化合物）组合，构建金属配合物/手性分子共催化体系，将过渡金属配合物光催化剂对底物分子SP3 C-H键的活化作用与手性分子对底物分子或活化中间体的不对称诱导作用结合起来，研究催化剂性能，探讨反应机理。在此基础上，选择光谱响应范围较宽的大分子共轭物质作为光敏剂，与手性有机分子构成双功能光催化剂，研究它们的应用性能，进一步为不对称催化反应提供新的高效绿色催化技术。

Asymmetric reaction for the synthesis of chiral compounds by cooperative organocatalysis and visible-light photocatalysis is a new way to use solar energy. In this project, a series of electron-rich organic ligands will be designed for the formation of copper, iron and other cheap transition-metal complexes to be used as visible-light photocatalysts. These new materials should have stable chemical properties，long excited-state lifetime as well as high redox potential. Through the combined use of organic small-molecule chiral catalysts (such as chiral amines and thioureas) and the as-designed metal complexes, a dual catalytic system can be established. The objective is to combine photocatalytic activation of sp3 C-H bond together with asymmetric induction to substrates or activated intermediates. The performance of this metal complexes/chiral molecules system will be evaluated over selected organic reactions of asymmetric nature, and the related mechanisms studied. On this basis, commercial conjugated macromolecules with wide spectral response range will be adopted together with selected chiral organic molecules for the generation of this class of bifunctional catalysts. It is envisaged that a green technology based on organocatalysis and visible-light-induced photoredox catalysis will be developed for efficient synthesis of asymmetric organic compounds.