The design and synthesis of a C2-sym. chiral 1,2-bis(diphenylphosphino)benzene ligand via the Rh-catalyzed intramol. [2 + 2 + 2] cycloaddn. followed by redn. are disclosed. This new chiral dppbz-type ligand could be employed for the Rh-catalyzed asym. alkene hydrogenation. [on SciFinder(R)]