Abstract The isomerization of N, O-acetals 1 yields N-acyl-O-vinyl acetals 2 or 2- aminomethyl-1, 3-butadienes 10, depending on the nature of the nitrogen substituents. In the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) the N, O-acetals 2h–u are converted stereoselectively into β-(N-acylamino) aldehydes 3. The relative configurations of the products 3 have been determined by X-ray analysis and 1 H-NMR experiments. The ...