氧气参与钯催化烯烃双官能团化方法研究

Inspired by the need for green and sustainable chemistry, modern synthetic chemists have been seeking general and practical ways to construct complex molecules while maximizing atom economy and minimizing synthetic steps. Considerable progress has been made to fulfill these goals by taking advantage of transition-metal-catalyzed transformations with diverse and tunable reactivities. Particularly, difunctionalization reactions of alkenes under molecular oxygen have been systematically studied based on the principle of “green chemistry”. This project used substituted imidazole as starting material. By introducing containing oxygen, sulfur and nitrogen atom functional groups to prepare the task ionic liquids with special physical and chemical properties. Furthermore, design and preparation the palladium and copper metal clusters with the ionic liquids as the ligands. Then, exploring the catalytic activity and the reaction mechanism of those metal clusters in difunctionalization reactions of the electron-rich alkenes, developing a series of green, efficient, highly selective olefin difunctionalization reaction for synthesis of a variety of natural products, pharmaceuticals, pesticides, as well as functional materials. .This projects not only could develop a transition-metal-catalyzed difunctionalization of electron-rich alkenes, but also could enlarge the organic synthetic chemistry and the green chemistry.

实现绿色、高效、高选择性的合成与转化是具有挑战性和战略性意义的研究课题，其中过渡金属催化的烯烃双官能团化反应一直是有机合成化学研究中最为活跃的领域之一，特别是在绿色氧化剂——氧气中进行的过渡金属催化反应因其环境友好和高原子经济性而倍受关注。本项目以取代的咪唑为起始原料，通过引入含有氧、硫、氮等官能团，制备具有特殊物理和化学性质的功能化离子液体。同时，设计、制备功能化离子液体与钯、铜等过渡金属的簇合物，探索金属簇合物在烯醇、烯胺、烯醚等富电子烯烃的双官能团化反应中的催化活性及作用机制，进而发展系列绿色、高效、高选择性的烯烃双官能团化反应，为合成多种具有潜在生物活性的氮杂或氧杂分子骨架奠定基础。项目的完成不仅可以发展过渡金属催化烯烃双官能团化反应的新方法、新技术，而且还将丰富有机合成化学和绿色有机化学的内涵。

过渡金属催化的烯烃双官能团化反应是有机合成化学研究中最为活跃的领域之一。离子液体作为绿色溶剂，因在其中进行的偶联机理和途径可能不同于传统的分子溶剂亦被广泛研究。项目在氧气氛围中，以离子液体为绿色介质及催化剂的配体，探索钯催化剂在烯醇、烯醚等富电子烯烃的双官能团化反应中的催化活性及作用机制，发展系列底物适用范围广、条件温和、绿色的新策略、新方法合成具有潜在生物活性的骨架分子。比如，发展了氯钯化启动的炔卤和未活化烯烃分子间串联的碳醚化反应，高效、高选择性地构建官能团化的氧代环丁烷化合物(Org. Chem. Front., 2017, 4, 373)，并被Synfacts亮点介绍。参编著作一部“Pd-catalyzed Heterocycle Synthesis in Ionic Liquids, P351-368.”《Ru-, Rh-, Pd-catalyzed Heterocycle Synthesis》, Edited by: Xiao-Feng Wu World Scientific Press, 2016。由于在离子液体方面比较系统的研究工作，应邀在Eur. J. Org. Chem.上发表题为“Recent advances in Pd-catalyzed cross-coupling reaction in ionic liquids”综述性文章(Eur. J. Org. Chem., 2018, 1284)。应邀在第十四届全国均相催化学术会议和第七届岭南有机化学论坛上作“离子液体中钯催化烯炔交叉偶联反应”学术报告。带有基金号的(21502055)相关研究成果17篇，发表在J. Org. Chem.、ACS Sustainable Chem. Eng., Org. Chem. Front., Adv. Synth. Catal.等国际国内化学领域主流杂志上。