亚砜配体在金属催化烯丙基官能团化反应中的应用

Development of sulfoxide ligand for metal-catalyzed allylic functionalization

过渡金属催化的烯丙基官能团化反应在有机合成中具有重要作用,是构建碳碳键和碳杂原子键的重要方法。亚砜配体以其独特的立体化学性质,不仅在传统的(Tsuji-Trost)烯丙基取代反应中取得优异结果,而且在烯丙基C—H活化反应中展现出巨大潜力。根据烯丙基钯中间体的催化反应机理及亚砜配体配位模式,总结了近些年亚砜配体在传统的烯丙基取代、烯丙基C—H官能团化及不对称烯丙基C—H官能团化领域的最新研究进展,指出了影响各个催化体系的关键因素及所存在的问题,并对今后发展作出了展望。

Transition metal catalyzed allylic functionalization reactions play an important role in organic synthesis and are important methods to construct carbon-carbon bonds and carbon-heteroatom bonds. Due to their unique stereochemical properties, sulfoxide ligands achieve excellent results in traditional(TsujiTrost) allylic substitution reactions and display great potential in the allylic C—H activation reactions.According to the catalytic reaction mechanism of allylic palladium intermediates and the coordination mode of sulfoxide ligand, the research progress of sulfoxide ligands in the traditional allylic substitution, allylic C—H functionalization and asymmetric allylic C—H functionalization in recent years is summarized. The key factors and existing problems affecting each catalytic system are pointed out and the future development is prospected.