Zinc‐Catalysed N‐Iodosuccinimide‐Enabled Selective N2‐Olefination of Benzotriazoles with Alkenes

Herein, we describe a zinc‐catalysed N2‐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 N2‐selective β‐iodoalkylation of benzotriazoles is highly stereospecific and works under very simple and mild conditions, exhibiting excellent functional group tolerance. The high N2‐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 N2‐olefinated benzotriazoles, will significantly contribute to the chemistry of N2‐functionization of benzotriazoles. magnified image