The oxidative alkenylation reaction of α-aminoalkyl C(sp3)-H bonds has been investigated with (E)-1,2-bis(sulfonyl)ethenes. The catalytic process of iron-polypyridyl complexes drives the single-electron oxidation of dialkyl anilines, resulting in the formation of α-aminoalkyl radical species. Subsequent cascades of radical addition and elimination reactions ensue, ultimately leading to the generation of sulfonylated allylic amine products. The utility of these products extends further, enabling the synthesis of multisubstituted heterocycles like pyrroles, pyrazines, and triazoles.