膦配体电子和空间效应对钯催化羰化酯化反应的影响

Influence of Electronic and Steric Factors of Phosphine Ligands upon Palladium-catalyzed Alkoxycarbonylation

膦配体修饰的钯催化剂在不饱和化合物羰化酯化反应中使用广泛,其催化活性在很大程度上取决于金属周围的配体环境.膦配体电子和空间效应的调变,可以实现定向催化,甚至可以预测催化行为.新催化反应的开发和现有催化反应的优化都可以通过膦配体的合理设计来实现.配体已经成为了公认的最重要的需要详细研究的变量之一.我们综述了钯催化烯烃羰化酯化反应中,单齿膦配体、双齿膦配体、半稳定膦配体电子和空间效应对活性和选择性的调控作用,并对面临的问题和未来的发展方向进行了探讨,以期对未来设计高效高选择性羰化酯化反应催化体系提供指导.

Palladium catalysts modified with phosphine ligands are widely used in the alkoxycarbonylation of unsaturated compounds,and their catalytic activity largely depends on the coordination environment around the metal center.The modulation of electronic and steric effects of phosphine ligands can achieve directional catalysis and even predict the catalytic behavior.Moreover,the development of new catalytic reactions and the optimization of existing ones can be achieved through the rational design of phosphine ligands.Ligand is already recognized as one of the most important variables requiring detailed study.The regulation of activity and selectivity based on electronic and steric effects of phosphine ligands,including monodentate,bidentate and hemilabile ligands,in palladium-catalyzed alkene alkoxycarbonylation is reviewed.Furthermore,we discuss the facing problems and future prospects in order to provide guidance for the design of efficient and high-selectivity alkoxycarbonylation catalytic systems.