Synthesis of Sulfilimines via Visible‐Light‐Mediated Triplet Energy Transfer to Sulfonyl Azides

Sulfilimines and their derivatives have garnered considerable interest in both synthetic and medicinal chemistry. Photochemical nitrene transfer to sulfides is known as a conventional synthetic approach to sulfilimines. However, the existing methods have a limited substrate scope stemming from the incompatibility of singlet nitrene intermediates with nucleophilic functional groups. Herein, we report the synthesis of N‐sulfonyl sulfilimines via visible‐light‐mediated energy transfer to sulfonyl azides, uncovering the previously overlooked reactivity of triplet nitrenes with sulfides. This reaction features broad functional group tolerance, water compatibility, and amenability to the late‐stage functionalization of drugs. Thus, this work represents an important example of energy transfer chemistry that overcomes challenges in traditional synthetic methods. We report a novel reactivity of triplet nitrenes toward sulfides to afford sulfilimines. The use of triplet nitrenes as reactive intermediates circumvented the substrate scope limitations of the prior singlet nitrene approaches, as demonstrated by broad functional group tolerance, water compatibility, and amenability to use for the late‐stage functionalization of drugs.