An extremely efficient method has been found for the catalytic asymmetric hydrogenation of conjugated alpha,gamma-dienamide esters using the Et-DuPHOS-Rh catalyst system. alpha,gamma-Dienamide ester substrates were prepared via the Suzuki cross-coupling reaction and the Horner-Emmons olefination. Full conversion to the corresponding gamma,delta-unsaturated amino acids with very high regio-and enantioselectivity was achieved after short reaction times. This new methodology was applied to the synthesis of the natural product bulgecinine from a prochiral dienamide ester.