Abstract The mechanism of the homogeneously catalyzed hydrogenation of 1, 3- oxazolidines with a Rh (I) diphosphane catalyst affording tertiary hydroxyethyl-substituted amines was investigated with the help of D 2 labelling experiments. It was found that the reaction proceeds via prochiral intermediates with, preferentially, an iminium cation being in equilibrium with the 1, 3-oxazolidine. This observation opened up the opportunity to run ...