Use of a typical rhodium precatalyst for hydroformylation results in the enantioselective hydrogenation of cyclic enones with up to 90% ee. Extensive screening of chiral ligands reveals the simple ligand Chiraphos as the best ligand, so far. The hydrogenation shows high chemoselectivity. Exclusive formation of saturated, chiral b-branched ketones is observed. It is proposed that the catalyst follows a frustrated hydroformylation pathway ("monohydride-based mechanism") and differs by that from the classical cationic Schrock-Osborn type rhodium precatalysts ("dihydride-based mechanism") for enantioselective hydrogenation. The catalyst operates under neat conditions and is easily recyclable by simply distilling off the reaction mixture and treatment with syn gas prior to hydrogenation.