Over the past few years, significant research has been directed toward the development of new methods for synthetic efficiency and atom economical processes. Among them, the potential of transition-metal catalyzed reactions has been steadily demonstrated, as they provide a direct and selective way toward the synthesis of highly valuable products. We have been engaged in a project dedicated to the development of catalytic methods for the synthesis of biorelevant targets. More specifically, we have been interested in hydrogenation and transfer hydrogenation reactions, which provide important catalytic approaches to fine chemicals. There is no doubt that chiral ligands are at the heart of any enantioselective homogeneous process. In this context, our contribution to this field is the development of atropisomeric diphosphanes named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. Some recent applications in this field will be presented.