The unprecedented N-heterocyclic carbene. (NHC)-catalyzed intermolecular cross-coupling of enamides and aldehydes is described. Upon exposure of enamides to aldehydes in the presence of a NHC catalyst, catalytic C-C bond formation occurs, providing highly enantioselective N-protected amines, bearing a quaternary carbon center, in good yields and with high enantioselectivities.