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

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