Enantioselective reduction of acylphosphines, after precomplexation with borane, proceeded smoothly in the presence of a chiral oxazaborolidine catalyst and catecholborane. α-Hydroxyalkylphosphine products were obtained as phosphine–borane complexes in good yield and enantioselectivity. One of the products of the enantioselective reduction was successfully applied as an optically active phosphine ligand for asymmetric catalysis after suitable derivatization.

Practical and versatile syntheses of tertiary phosphine derivatives have been achieved by palladium-catalyzed deformylative P–C cross-coupling reactions of hydroxymethylphosphine derivatives. Sequential couplings of orthogonally protected precursors provide a simple and practical route toward a variety of tertiary phosphine derivatives having aryl substituents in any combination.