We report herein the Pd-catalyzed P-C cross-coupling reaction between enol phosphates and secondary phosphane-borane complexes or phosphane oxides. The reaction was performed under mild conditions, owing to Pd activation of the P-H bonds of the phosphane-boranes (or phosphane oxides) and to the powerful enol phosphate coupling reagents. New useful chiral and achiral α-β- alkenylphosphane derivatives bearing an amido group in the α-position to the P center were obtained in yields up to 70 %. A useful and versatile Pd-catalyzed P-C cross-coupling reaction was applied with success to a range of secondary phosphane-borane or phosphane oxide derivatives and α-amido enol phosphate reagents. The reaction afforded new chiral or achiral tertiary α-enamido phosphane derivatives.