Generation of the SCF3 Radical by Photoredox Catalysis: Intra‐ and Intermolecular Carbotrifluoromethylthiolation of Alkenes. Issue 18 (13th March 2017)

• Record Type: Journal Article
• Authors: Dagousset, Guillaume; Simon, Cédric; Anselmi, Elsa; Tuccio, Béatrice; Billard, Thierry; Magnier, Emmanuel
• Is Part Of: Chemistry. Volume 23:Issue 18(2017)
• Page Start: 4282
• Page End: 4286
• Publication Date: 2017-03-13
• Subjects: carbotrifluoromethylthiolation -- EPR spectroscopy -- photoredox catalysis -- radicals -- trifluoromethylthiosaccharin; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201700734
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: We report the first use of N ‐trifluoromethylthiosaccharin as the source of SCF3 radical under photoredox catalysis. This allowed an efficient and general visible‐light‐mediated carbotrifluoromethylthiolation of alkenes. Under the optimized conditions using fac ‐[Ir(ppy)3 ] as the photocatalyst, various N ‐aryl acrylamides as well as a wide range of substituted styrenes can readily be difunctionalized in an intra‐ or intermolecular fashion, affording the corresponding SCF3 ‐containing products in good to excellent yield. Importantly, the formation of this SCF3 radical along with other key radical intermediates was unambiguously demonstrated thanks to spin trapping/electron paramagnetic resonance (ST/EPR) experiments, which enabled a clear understanding of the reaction mechanism. Abstract : Electrophilic N ‐trifluoromethylthiosaccharin was used for the first time as the source of the SCF3 radical. The formation of this radical, as well as other key intermediates, was highlighted by using spin trapping/EPR spectroscopy. Visible‐light‐promoted intra‐ and intermolecular carbotrifluoromethylthiolation of alkenes has been successfully developed.