Metal-Free Aziridination of Unactivated Olefins via Transient N-Pyridinium Iminoiodinanes

We describe a metal-free aziridination of unactivated olefins to generate N-pyridinium aziridines, which participate in cross-coupling to afford N-aryl aziridines and reductive depyridylation to afford N–H aziridines. Kinetics experiments, based on variable time normalization analysis (VTNA), indicate that aziridination proceeds via a highly electrophilic N-pyridinium iminoiodinane intermediate. These studies expand build-and-couple strategies for aziridine synthesis to unactivated olefins and introduce charge-enhanced electrophilicity to the chemistry of iminoiodinanes.