Enantiomerically enriched sulfonamides were synthesized by the radical addition of an acetal to enantiomerically pure N -sulfinyl imines using dimethylzinc–air and boron trifluoride diethyl etherate. Higher levels of stereocontrol were observed by using a mesitylenesulfinyl group. Furthermore, an amine and an amino alcohol with high enantiomeric purity were obtainable from the sulfonamide product.