Rhodium complexes of P-OP ligands serve as highly efficient and enantioselective catalysts in asymmetric hydrogenation leading to various valuable pharmaceutical building blocks and several direct precursors of chiral drugs such as LY2497282, lacosamide, rivastigmine, and aprepitant and 12 further examples (see scheme; nbd=norbornadiene; XC(O)G=NHAc, NHBoc, NHCbz, 2-oxopyrrolidin-1-yl, OAc).