非金属试剂/氧气体系促进的经历自由基正离子过程的反应研究

This project proposes to activate reaction substrates using non-metallic reagent under aerobic condition to generate radical cation intermediates, which then convert to carbocation or radical intermediates for further reactions. This project begins with the exploration of oxidative dehydrogenative coupling reactions and will expand to develop various synthetically useful methodology. We will focus on the development of new reactions that need small catalytic amounts of nonmetallic promotors under mild conditions with good generality and scope. Their mechanism and the application in the synthesis of complex molecules will be explored too. The study will be helpful for the understanding the nature of the aerobic radical cation mediated reactions and explore its applications in organic synthesis.

本次申请拟通过催化量的非金属试剂在氧气存在条件下活化反应底物，生成自由基正离子中间体，进而转化为碳正离子或自由基中间体发生后续反应。以探索非金属试剂/氧气条件下的氧化脱氢偶联反应为切入点，进行具有合成价值的反应方法学研究。重点是发展促进剂用量小、操作简便、条件温和、具有较广阔底物适应性的新反应，并探索其反应机理及其在复杂分子合成中的应用。此研究的进行有助于深入理解和认识有氧条件下经历自由基正离子过程的反应的本质和规律，并拓宽其在有机合成中的应用。

通过单电子氧化方式活化底物分子，进而脱氢生成碳正离子中间体，与亲核试剂反应构建碳碳键以及碳杂原子键，合成复杂有机化合物分子。