Access to Cyclic N‑Trifluoromethyl Ureas through Photocatalytic Activation of Carbamoyl Azides

• Published in: Journal of the American Chemical Society Vol. 144; no. 13; pp. 6100 - 6106
• Main Authors: Bouayad-Gervais, Samir, Nielsen, Christian D.-T., Turksoy, Abdurrahman, Sperger, Theresa, Deckers, Kristina, Schoenebeck, Franziska
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06-04-2022
• Subjects: Azides - chemistry; Catalysis; Light; Nitrogen - chemistry; Oxidation-Reduction
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.2c02004

We report the mild activation of carbamoyl azides to the corresponding nitrenes using a blue light/[Ir]-catalyzed strategy, which enables stereospecific access to N-trifluoromethyl imidazolidinones and benzimidazolones. These novel structural motifs proved to be highly robust, allowing their downstream diversification. On the basis of our combined computational and experimental studies, we propose that an electron rebound with the excited metal catalyst is undergone, involving a reduction-triggered nitrogen loss, followed by oxidation to the corresponding carbamoyl nitrene and subsequent C–H insertion.