Zinc‐Catalysed N ‐Iodosuccinimide‐Enabled Selective N 2 ‐Olefination of Benzotriazoles with Alkenes

Herein, we describe a zinc‐catalysed N 2 ‐selective olefination of benzotriazoles with unactivated alkenes and styrenes. The transformation is achieved by a N ‐iodosuccinimide (NIS)‐mediated two‐step, one‐pot approach, proceeding through sequential regioselective β ‐iodoalkylation of benzotriazoles with alkenes and a subsequent base‐promoted 1,2‐elimination. The N 2 ‐selective β ‐iodoalkylation of benzotriazoles is highly stereospecific and works under very simple and mild conditions, exhibiting excellent functional group tolerance. The high N 2 ‐selectivity is attributed to intermolecular hydrogen bonding between the N ‐iodosuccinimide and the NH hydrogen bond donor at the 1‐position of the benzotriazoles. This scalable process, serving as an efficient method for modular assembly of structurally diverse N 2 ‐olefinated benzotriazoles, will significantly contribute to the chemistry of N 2 ‐functionization of benzotriazoles.