Thiolane Sulfoximines as Azide Surrogates for Quinolyl Nitrenes: Photochemical Access to Ortho ‐Diaminoquinolines
Abstract
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.
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BibTeX
@article{serusi2026thiolane,
title = {{Thiolane Sulfoximines as Azide Surrogates for Quinolyl Nitrenes: Photochemical Access to Ortho ‐Diaminoquinolines}},
author = {Lorenzo Serusi and Timothé Maujean and Camille Van Wesemael and Romain Pertschi and Vicenç Branchadell and Mihaela Gulea},
journal = {Advanced Synthesis and Catalysis},
year = {2026},
month = oct,
doi = {10.1002/adsc.70813},
url = {https://hal.science/hal-05844952v1},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Thiolane Sulfoximines as Azide Surrogates for Quinolyl Nitrenes: Photochemical Access to Ortho ‐Diaminoquinolines
AU - Lorenzo Serusi
AU - Timothé Maujean
AU - Camille Van Wesemael
AU - Romain Pertschi
AU - Vicenç Branchadell
AU - Mihaela Gulea
PY - 2026
DA - 2026/10/19
JO - Advanced Synthesis and Catalysis
DO - 10.1002/adsc.70813
UR - https://hal.science/hal-05844952v1
AB - 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.
SN - 1615-4150
SN - 1615-4169
ER -