A new palladium(II) complex containing an amido-substituted P-chiral phosphine ligand is prepared efficiently by the asymmetric Diels-Alder reaction between N,N-dimethylacrylamide and 1-phenyl-3,4-dimethylphosphole; the chelating properties of the functionalised ligand and the absolute configurations of the four newly generated stereocentres are determined by single-crystal X-ray analysis, and the optically active phosphine ligand displaced from the palladium template with 1,2-bis(diphenylphosphino)ethane.