The monograph provides the reader with a broad view of the challenges and opportunities related to the use of phosphine ligands in stereoselective catalytic hydrogenation. The structure of the title compounds offers a range of possibilities related to the choice of the type of chirality, as well as their modification and substitution. This is to develop a unique structure that works with maximum asymmetric induction under certain conditions. The selection of these conditions is an optimization process running in parallel with the development of the ligand structure. The results of such studies are in many cases striking in terms of scientific quality, and the result of a series of iterative processes is the development of processes leading to practically enantiomerically pure products, often bioactive.