Metal Additive–Free Iodine–Promoted Reorganization of Ynamide‐Ynes and Stereoselective 1,2‐Diiodination

We report a metal additive–free iodine‐promoted one‐step structural reorganization of ynamide‐ynes and simultaneous stereoselective 1,2‐diiodination of the migrated alkyne to form stereospecific tetrasubstituted alkenyl diiodo‐tethered indoles (E‐isomer). Molecular iodine is cost effective, user friendly, less toxic, commercially available, and easy to handle. The key features of the reaction include metal– and additive–free environment, selectivity, structural reorganization, mild reaction conditions, simple workup, and gram‐scale synthesis. This transformation generates multiple bonds [nitrogen (N)–carbon (C)sp2, Csp2–Csp2, 2 Csp2–iodine (I)] via N–Csp bond cleavage in ynamide‐ynes.