Abstract A variety of N‐heterocyclic derivatives were synthesized by iodine‐mediated aminative difunctionalization/cyclization of N ‐alkenyl sulfonamides. The present synthetic process involves nitrogen‐centered radicals generated from sulfonamide precursors. It is operationally simple and amenable to gram‐scale synthesis under transition‐metal‐free conditions. The reaction is applicable to the synthesis of iodinated N‐heterocyclic products in the absence of disulfides/diselenides and also to the preparation of thiolated/selenylated products in their presence, respectively.