Abstract The rhodium-catalyzed asymmetric hydrogenation of different acyclic and cyclic N- acyl enamides to give N-acyl-protected optically active amines has been examined for the first time in detail in the presence of chiral monodentate 4, 5-dihydro-3H- dinaphthophosphepines 5a–i. The enantioselectivity is largely dependent on the nature of the substituent at the phosphorus atom and the enamide substrate. Applying optimized ...