钌催化芳烃间位高位点选择性的C-H/Si-H脱氢偶联反应研究及应用

芳基硅烷衍生物在材料、医药和合成化学等领域都有重要应用，因此这类化合物的高效构建一直是有机合成化学的热门研究课题之一。然而，目前建立的合成方法在原子经济性和位点选择性方面大都不够理想，近期发展的过渡金属催化芳烃C-H键活化的策略也只能实现导向基团邻位C-Si键的构建。与此同时，高效、高位点选择性反应的开发受到了研究人员越来越多的关注。因此，开发芳烃间位高位点选择性的C-H键硅烷化反应是一项重要且具有挑战性的课题。本项目拟探究钌催化芳烃导向基团间位高位点选择性的C-H/Si-H交叉脱氢偶联反应，发展间位C-H键活化构建C-Si键的新途径。通过研究反应过程中可能涉及的活性环钌中间体和硅自由基物种，揭示反应机理，建立合理的催化循环。此外，间位硅烷化芳烃的转化反应将为芳烃间位C-H键官能团化反应的发展提供重要途径。

Arylsilane derivatives possess important applications in materials, medicine, and synthetic chemistry. Therefore, the efficient construction of such compounds has always been one of the hot research topics in synthetic organic chemistry. However, the currently established synthetic methods are mostly unsatisfactory in terms of atom economy and site selectivity. The recently developed transition metal-catalyzed C-H bond activation strategy for aromatic hydrocarbons can only achieve the construction of the ortho-position C-Si bond of the guiding groups. At the same time, the development of efficient and highly site-selective reactions has attracted more and more attention from researchers. Therefore, it is an important and challenging subject to develop silanization reactions of the meta C-H bonds of aromatic hydrocarbons with high site selectivity. This project intends to explore the ruthenium-catalyzed C-H/Si-H cross dehydrogenation coupling reactions at the meta position of the guiding groups of aromatic hydrocarbons with high site selectivity, and develop a new way to activate the meta-C-H bond to construct C-Si bonds. By studying the active ring ruthenium intermediates and silicon radical species that may be involved in the reaction process, the reaction mechanism will be revealed and a reasonable catalytic cycle will be established. In addition, the conversion reactions of meta-silanized aromatic hydrocarbons will provide an important way for the development of meta-C-H bond functionalization reactions of aromatic hydrocarbons.