Rhodium(II)-Catalyzed Dehydrogenative Silylation of Biaryl-Type Monophosphines with Hydrosilanes

A rhodium-catalyzed system is introduced for in situ modification of biaryl-type monophosphines with hydrosilanes through a P-III-chelation-assisted dehydrogenative silylation reaction. A series of ligands containing silyl groups with different steric and electronic properties were obtained with excellent regioselectivities. This method offers many advantages, including the use of commercially available phosphines, no requirement for an external ligand or oxidant, a broader substrate scope, high efficiency, and access to a single regioisomer. Based on the outstanding properties of the parent scaffolds, the silyl-substituted phosphines serve as excellent ligands in Pd-catalyzed asymmetric Suzuki coupling reactions.