A General Nitrene Transfer to Sulfides Enabled by 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 a general nitrene transfer for the synthesis of N-sulfonyl sulfilimines enabled by visible-light-mediated energy transfer to sulfonyl azides, uncovering the neglected reactivity of triplet nitrenes with sulfides. The unprecedented mechanism involving single electron transfer enabled broad functional group tolerance, water compatibility, and amenability to use for the late-stage functionalization of drugs.