Donor-acceptor monosubstituted hydrazone's participate as suitable reagents able to undergo an enantioselective formal diaza-ene reaction with alpha,beta-unsaturated aldehydes under chiral secondary amine catalysis. This constitutes a new approach for the enantioselective conjugate addition of hydrazones to enals under metal-free conditions and leads to the formation of gamma-hydrazono carboxylic acids after oxidation/[1,3]-H shift. The methodology is also useful for the synthesis of enantioenriched beta-substituted alpha-keto-1,5-diesters by using the hydrazone moiety as a masked carbonyl group.