A major trend in fine chemicals and pharmaceuticals is the synthesis of molecules with increased complexity. This trend translates the aim of organic syntheses to conditions in which high degrees of chemo-, regio- and stereoselectivity can be provided. In this context, the chemoselective hydrogenation of one functional group in the presence of other reactive groups is a frequently encountered problem in fine chemicals manufacture. This study provides a critical analysis including elegant examples of reactions in which high chemo- and diastereoselectivities were achieved in the hydrogenation of a C=O group in the presence of C=C double bond. A particular emphasis is addressed to the stereoselective C(15) synthesis from Cloprostenol--a PGF2α structural analogue.