AbstractOrganophosphines are an important class of ligands widely used in organic chemistry. Although great progress has recently been made in the rapid construction of new phosphines through Rh- or Ru-catalyzed C–H bond functionalizations, synthetic access to more diverse phosphines remains a challenge. We describe an efficient process for the rhodium-catalyzed phosphorus(III)-directed hydroarylation of internal alkynes to generate various alkenylated and 2′,6′-dialkenylated biarylphosphines with high selectivity. A range of diverse alkynes and phosphines were effectively prepared with broad functional-group compatibility under the optimized conditions. In addition, the developed protocol can be extended to modify chiral phosphine ligands, providing enantioenriched alkenylated phosphines without erosion of the enantiomeric excess.
