Divergent Reactions between Alkynes and Dibenzenesulfonimide: Selective Synthesis of Ynamides and Enamides under Metal‐Free Conditions

Abstract Divergent reactions between alkynes and dibenzenesulfonimide that can generate ynamides and enamides selectively are reported. Oxidative C(sp)−H bond amidation of various arylacetylenes occurred in the presence of a hypervalent iodine reagent to form the corresponding ynamides. Without any catalyst or oxidant, direct hydroamidation occurred to produce regioselective Markovnikov's enamides. Both reactions proceeded under facile, neutral, and metal‐free conditions and possessed the merit of stable performance and easy operation.