Fluorinated Sulfilimino Iminiums: Efficient and Versatile Sources of Perfluoroalkyl Radicals under Photoredox Catalysis. Issue 14 (2nd March 2017)

• Record Type: Journal Article
• Authors: Daniel, Marion; Dagousset, Guillaume; Diter, Patrick; Klein, Pierre‐André; Tuccio, Béatrice; Goncalves, Anne‐Marie; Masson, Géraldine; Magnier, Emmanuel
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 14(2017)
• Page Start: 3997
• Page End: 4001
• Publication Date: 2017-03-02
• Subjects: EPR spectroscopy -- fluoroalkylation -- photochemistry -- radicals -- reaction mechanisms; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201700290
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reported herein is the use of S‐perfluoroalkyl sulfilimino iminiums as a new source of RF radicals under visible‐light photoredox catalysis (RF =CF3, C4 F9, CF2 Br, CFCl2 ). These shelf‐stable perfluoroalkyl reagents, readily prepared on gram scale from the corresponding sulfoxide using a one‐pot procedure, allow the efficient photoredox‐induced oxyperfluoroalkylation of various alkenes using fac‐Ir(ppy)3 as the photocatalyst. Importantly, spin‐trapping/electron paramagnetic resonance experiments were carried out to characterize all the radical intermediates involved in this radical/cationic process. Abstract : Rad source : S‐Perfluoroalkyl sulfilimino iminiums were used as a new source of perfluoroalkyl radicals (RF =CF3, CF2 Br, C4 F9, CFCl2 ). The formation of these radicals, as well as other key intermediates, was highlighted by spin‐trapping/EPR spectroscopy. Visible‐light‐promoted three‐component oxyperfluoroalkylation of alkenes was successfully developed. ppy=2‐phenylpyridine.