Biarylphosphines have been widely applied as ligands in various synthetic methods, especially in transition-metal-catalysed carbon-carbon and carbon-heteroatom bond cross-coupling reactions. Based on the outstanding properties of the parent scaffolds, a general method for in situ modification of the commercial tertiary phosphine ligands to access a series of ligands is in high demand. Here we show that a rhodium-catalysed system is introduced for the hydroarylation of alkenes and alkynes with tertiary phosphines through P(III)-chelation assisted C-H activation. A series of ligand libraries containing alkyl and alkenyl substituted groups with different steric and electronic properties are obtained in high yields. Furthermore, several experimental studies are performed to uncover the key mechanistic features of the linear-selective hydroarylation of alkenes and branch-selective hydroarylation of alkynes.

联芳基膦已广泛用作各种合成方法中的配体，尤其是在过渡金属催化的碳-碳和碳-杂原子键交叉偶联反应中。基于母体支架的优异性能，对用于商业化叔膦配体的原位修饰以获取一系列配体的通用方法的需求很高。在这里，我们显示了通过P（III）螯合辅助的CH活化，将铑催化的体系引入用于将烯烃和炔烃与叔膦进行氢芳基化。以高收率获得了一系列包含具有不同空间和电子性质的烷基和烯基取代基的配体库。此外，