Summary The reactivity of (−)-ephedrine (2) and (+)-norpseudoephedrine (3) towards the amidacetals 1 a/b has been studied. Both 2 and 3 were acetylated resp. formylated at first at the amino group. Nevertheless, derivatives of 2 and 3 possessing a trisubstituted amino group react with 1 a in a [3.3] sigmatopic rearrangement to ortho substituted dimethylcarbamoylmethyl derivatives. By subsequent reduction with ...