Synthesis of P-Stereogenic Phosphinamides via Nickel-Catalyzed Kinetic Resolution of H-Phosphinamides by Alkenylation and Arylation.

A nickel-catalyzed enantioselective cross-coupling for the synthesis of P-stereogenic phosphinamides has been developed. The asymmetric alkenylation and arylation of racemic H-phosphinamides using alkenyl and aryl bromides resulted in the formation of P-stereogenic N-phosphinyl compounds with good yields and high enantioselectivities. This method tolerates a variety of functional groups, and its applications are explored through scale-up reactions and product transformations.