This Account outlines our efforts in the design and synthesis of a family of highly effective atropisomeric dipyridylphosphine ligands (P-Phos and its variants) and in the development of their widespread applications in transition-metal-catalyzed asymmetric reactions including hydrogenation, hydrosilylation, and C-C bond formation. Desirable attributes, such as air stability, broad substrate scope, fast rates of reaction, excellent enantioselectivities, low catalyst loading, and mild conditions, make the catalyst systems highly attractive and thus may provide excellent opportunities for practical applications.
