Aminohalogenation of Alkenes Enabled by I(I)/I(III) Catalysis

Abstract An iodoarene-catalyzed aminohalogenation of alkenes is reported via an I(I)/I(III) catalytic cycle. This protocol enables the unified installation of Cl, Br, and I across diverse alkenes at room temperature, employing inexpensive halogen sources. Notably, aryl- and alkyl-substituted alkenes exhibit divergent regioselectivities, which are dictated by the interplay of steric and electronic effects, manifested as Markovnikov selectivity for aryl alkenes and sterically controlled attack for alkyl alkenes. Mechanistic studies support an electrophilic pathway involving a hypervalent imidoiodine intermediate.