In the hydrogenation of ketopantolactone, the (R,R) and (R,S) diastereomers of a new chiral modifier, pantoyl-naphthylethylamine, afforded 74 and 40% ee, respectively, to (R)-pantolactone. On the basis of NOE studies and theoretical calculations, the different properties of the diastereomers and in particular the effect of acid on the modifier structure are deduced from differences in conformational rigidity and steric constraint. In case of the (R,R)-diastereomer, a loose, extended structure in apolar solvent changes to a compact conformation via an additional intramolecular hydrogen bond, resulting in a more defined “chiral pocket� available for the reactant on the Pt surface.