Azetidinones with a sulfenyl group on the beta-lactam nitrogen atom show interesting biological activities as antimicrobial agents and enzyme inhibitors. We report in the present study a versatile synthesis of N-sulfenylated azetidinones starting from the corresponding N-bromo derivatives by means of the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) radical as the catalyst and disulfides. Preparation of N-halo-azetidinones was studied and optimized. The reactivity of N-bromo-azetidinone 2a as a model compound in the presence of TEMPO radical was investigated by NMR and electron paramagnetic resonance (EPR) spectroscopy studies. Optimization of the reaction conditions allowed the access of N-alkylthio- or N-arylthio-azetidinones from 55 to 92% yields, and the method exhibited a good substrate scope.
Giraldi V., Giunchino F., Casacchia M.E., Cantelli A., Lucarini M., Giacomini D. (2023). N-Sulfenylation of β-Lactams: Radical Reaction of N-Bromo-azetidinones by TEMPO Catalysis. JOURNAL OF ORGANIC CHEMISTRY, 88(20), 14728-14735 [10.1021/acs.joc.3c01759].
N-Sulfenylation of β-Lactams: Radical Reaction of N-Bromo-azetidinones by TEMPO Catalysis
Giraldi V.Primo
Investigation
;Lucarini M.Penultimo
Conceptualization
;Giacomini D.
Ultimo
Writing – Original Draft Preparation
2023
Abstract
Azetidinones with a sulfenyl group on the beta-lactam nitrogen atom show interesting biological activities as antimicrobial agents and enzyme inhibitors. We report in the present study a versatile synthesis of N-sulfenylated azetidinones starting from the corresponding N-bromo derivatives by means of the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) radical as the catalyst and disulfides. Preparation of N-halo-azetidinones was studied and optimized. The reactivity of N-bromo-azetidinone 2a as a model compound in the presence of TEMPO radical was investigated by NMR and electron paramagnetic resonance (EPR) spectroscopy studies. Optimization of the reaction conditions allowed the access of N-alkylthio- or N-arylthio-azetidinones from 55 to 92% yields, and the method exhibited a good substrate scope.File | Dimensione | Formato | |
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