Catalytic quantities of (R)- or (S)-1-(1-naphthyl)ethylamine induce up to 82% e.e. in the hydrogenation of ethyl pyruvate over Pt-alumina, the actual modifier responsible for enantioselection being the secondary amine resulting from imine formation with ethyl pyruvate and subsequent reduction of the C=N bond; a series of related derivatives has been prepared by reductive amination and tested as chiral modifiers.