Enantiomerically pure, alcohol-functionalized diphosphane ligands carrying one phosphorus and three carbon stereogenic centers were generated from the Diels-Alder reactions of phosphane-functionalized terminal alkenols [3-(diphenylphosphanyl)but-3-en-1-ol and 2-(diphenylphosphanyl)prop-2-en-1-ol] with 3,4-dimethyl-1-phenyl-1H-phosphole. The reactions were promoted and controlled by the organoplatinum complex containing ortho-metalated (R)-[1-(dimethylamino)ethyl]naphthalene, and both cycloadditions showed excellent regio-and stereoselectivity under mild conditions