钌催化导向基协助的芳烃远程硒化反应研究

Aromatic compounds are the main building blocks of molecular engineering, drug design, molecular electronics and organometallic chemistry, and it is an important but challenging topic to activate the desired C–H bond in an regioselectivity controllable manner. Ruthenium-catalysed meta-C–H functionalization is one of the key emerging strategies for regioselective functionalization of arenes, and has become a hot topic in this aera due to its high potential synthetic value. The development of novel reaction types, efficient catalytic systems and expand derived directing groups is still the scientific issue worthy of study in meta-C–H functionalization of arenes. Organic selenium compounds are commonly found in drug molecules and organic functional materials, and the development of green and efficient C–Se bond methods would be highly desirable. Recently, the directing group-assisted C2 selenation of arenes has been demonstrated, however, there is no report on the meta-C–H selenation of arenes. In view of the importance of organic selenium compounds and the novelty of the meta-C–H selenation of arenes, in this project, the challenging meta-, remote- and cross ring selenation of arenes assisted by directing groups, transition metal catalysts, ligands and additives will be explored.

芳烃是分子工程、药物设计、分子电子学以及金属有机化学的主要构建单元，实现芳烃分子中C–H键区域选择性可控的官能化反应，是芳烃化学中非常重要又极富挑战性的课题。钌催化芳烃间位导向的C–H键官能化反应，已经成为芳烃区域选择性官能化的一种重要策略，因其潜在合成价值，成为该领域的研究热点。发展新颖的反应类型，高效的催化体系和拓展可衍生化的间位导向基团依然是钌催化芳烃间位C–H键官能化反应中非常值得研究的科学问题。有机硒化合物常见于药物分子和有机功能材料中，发展绿色高效的构建碳硒键的新方法令人期待。目前，导向的芳烃邻位碳氢键的硒化反应相继被报道，而关于芳烃导向基间位碳氢键的硒化工作尚无报道。鉴于有机硒化合物的重要性和芳烃间位硒化反应的新颖性，本项目拟通过导向基、金属、配体以及添加剂等的调控，实现具有挑战性的杂原子导向的芳烃导向基间位、远程和跨环硒化反应。

含硒杂环因其重要的生物药理活性，成为化学、生物和医药领域的研究热点，发展合成含硒杂环的新方法是有机化学发展的前沿领域之一。现有含硒杂环的合成方法存在反应类型单一，产物结构多样性差等问题，无法满足结构新颖复杂的含硒杂环高效合成的需求。此外，含硒杂环活性靶点的鉴定工作鲜有研究，成为有机硒化学领域发展的瓶颈。目前，自由基硒化反应还远未被开发，发展潜力巨大。在我们小组前期不饱和键硒化双官能化工作基础之上，本项目以充分考虑硒中心自由基性质，从空间效应、电子效应以及环张力三个方面出发，合理设计底物和催化体系，实现了含硒二氟丁内酰胺制备，不对称硒醚制备以及有机硒催化的自由基接力叠氮化环化、aza-Wacker等反应；同时阐明此类反应的作用机制，最终为多样性有机硒化合物制备提供了实验支持和理论依据。