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

JACS Au. 2024 Oct 10;4(11):4187-4193. doi: 10.1021/jacsau.4c00556. eCollection 2024 Nov 25.

Abstract

We describe a metal-free aziridination of unactivated olefins to generate N-pyridinium aziridines. Subsequent cross-coupling affords N-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 N-pyridinium iminoiodinane intermediate. These studies expand build-and-couple aziridine synthesis to unactivated olefins and introduce charge-enhanced electrophilicity into the chemistry of iminoiodinanes.