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

Herein, visible‐light‐driven iron‐catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3)‐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. Visible‐light‐driven iron‐catalyzed nitrene transfer reactions with dioxazolones are used for intermolecular C(sp3)‐N, N=S and N=P bond formation. The key acyl nitrene iron intermediate is formed by conversion of the ground sextet state of dioxazolone‐bounding iron species to quartet spin state under visible‐light irradiation.