A new type of atropisomeric bisphosphine ligand 2 with a bridge across the 5, 5′-position of the biphenyl has been developed. The axial chirality of this type of ligands can be retained by macrocyclic ring strain produced from 5, 5′-linkage of the biphenyl even without 6, 6′-substituents on the biphenyls. Ligand (R)-2a showed good catalytic activity and enantioselectivity for Rh (I)-catalyzed asymmetric hydrogenation of (Z)-α- ...