Ariyarathna, Jeewani P; Baskaran, Prabagar; Chhikara, Akanksha; Kaur, Navdeep; Nguyen, Alex M; Premathilaka, Shashini; Huynh, Michelle M; Truong, Jonathon T; Li, Wei
N-heterocycles are privileged pharmaceutical scaffolds in drug discovery and development. We disclose here divergent intermolecular coupling strategies that can access diverse N-heterocycles directly from olefins. The radical-to-polar mechanistic switching is key for the divergent cyclization processes. These distinctive annulations result in the coupling of alkenes with simple bifunctional reagents for divergent N-heterocycle syntheses.