Copper-Catalyzed Addition of H–P(O) Bonds to Arynes

An efficient P-arylation of secondary phosphine oxides has been achieved through the ligand-free copper-catalyzed addition of H–P­(O) bonds to <i>in situ</i> generated arynes at room temperature. This transformation provides a straightforward route to the formation of the aryl–P bond with wide functional group compatibility, which produces arylphosphine oxides in up to 99% yield.