Thiolane Sulfoximines as Azide Surrogates for Quinolyl Nitrenes: Photochemical Access to Ortho ‐Diaminoquinolines

Quinolyl nitrenes are valuable reactive intermediates for the synthesis of nitrogen‐containing heterocycles but are commonly generated from hazardous azides under photochemical conditions. Herein, we introduce quinolyl thiolane sulfoximines as practical and thermally stable precursors for the photochemical generation of 8‐quinolyl nitrenes. Upon UV irradiation, these sulfoximines undergo selective S─N bond cleavage and react efficiently with primary and secondary amines, providing direct access to structurally diverse 7,8‐diaminoquinolines in moderate to excellent yields. The transformation releases tetramethylene S‐oxide as a small, benign, readily removable by‐product and exhibits broad functional‐group tolerance, including compatibility with amino acid derivatives, enabling the synthesis of valuable fused δ‐lactam scaffolds. DFT calculations support a mechanism involving nitrene formation followed by azirine trapping and rationalize the experimentally observed selectivity between diaminoquinoline and aminoazepine products. Overall, this work establishes quinolyl sulfoximines as practical and safer surrogates for azides in nitrene photochemistry, providing an efficient platform for the synthesis of 7,8‐diaminoquinolines.