Interweaving Visible‐Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones

Abstract Herein, visible‐light‐driven iron‐catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp 3 )‐N, N=S, and N=P bond formation are described. These reactions occur with exogenous‐ligand‐free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C−H amidations strategies, an intermolecular regioselective C−H amidation via visible‐light‐induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone‐bounding iron species to quartet spin state via visible‐light irradiation.