基于C(sp3)-H键活化的氧化偶联反应研究

过渡金属催化的惰性碳氢活化研究由于其独有原子经济性和环境友好特点已成为有机合成领域中最为活跃的前沿课题之一。相对于惰性C(sp2)?H键活化，C(sp3)?H键活化特别是无导向基团的惰性C(sp3)?H键活化研究挑战性更大。成功实现惰性C(sp3)?H键活化转化的关键之一是发展新型的C(sp3)?M键中间体成键方法。本项目将基于我们研究小组近期发展的碳自由基和低价金属发生单电子转移形成碳金属键这一策略，发展一系列过渡金属催化的基于无导向基团的C(sp3)?H键活化的氧化偶联反应，利用ESI-MS、NMR、HRMS及React-IR等现代分析测试手段和中间体的捕获技术，深入探讨成键反应中C(sp3)?H键选择性控制问题及C(sp3)?M键形成和转化机理，为新型C?H键活化模式的建立提供理论支持，合成出大量具有应用前景的功能有机分子。

Transition-metal-catalyzed inert C-H activation has become one of the most fascinating and challenging research topics in organic synthesis due to its atom economical and environmental friendly virtues. Catalytic inert C(sp3)?H bonds activation seems to represent a significantly bigger challenge compared to catalytic inert C(sp2)?H bonds activation. The key success to achieve catalytic activation inert C(sp3)?H bonds is the development of new strategies for the C(sp3)?M intermediate. This proposal will develop a series of oxidative coupling reactions by activation of inert C(sp3)?H bonds based on our new strategy for the activation of non-directed inert C(sp3)?H bonds, which is come from the fact that C(sp3)?M intermediate can be generated via a single-electron-transfer (SET) process between a free radical and a low valent metal. In our proposal, we will deeply study the interfering factors on the selectivity of the catalytic C(sp3)?H bonds activation, the generation and the transformation of the active C(sp3)?M intermediate by using intermediates trapping techniques and modern testing methods, such as ESI-MS, NMR, HRMS and React-IR, which will provide theoretical supports for the establishment of new catalytic C?H bonds activation modes. A large number of functional organic molecules will be synthesized by using our current approach.