The synthesis of optically and diastereomerically pure P-stereogenic phosphine-imidazole ligands is reported. The new ligands contain either a benzoimidazole or a 4-phenylimidazole as a N-donor fragment. The ligands were coordinated to iridium and the structure of the corresponding cationic COD complexes was detd. by x-ray anal. The combination of the chiral phosphorus atom and the imidazole substituents generate a strong chiral environment around the metal center. Preliminary hydrogenation reactions with a model cyclic β-enamide are also reported.