Fluorinated Sulfilimino Iminiums: Efficient and Versatile Sources of Perfluoroalkyl Radicals under Photoredox Catalysis

Marion Daniel; Guillaume Dagousset; Patrick Diter; Pierre-André Klein; Béatrice Tuccio; Anne-Marie Goncalves; Géraldine Masson; Emmanuel Magnier

doi:10.1002/anie.201700290

Fluorinated Sulfilimino Iminiums: Efficient and Versatile Sources of Perfluoroalkyl Radicals under Photoredox Catalysis

Angew Chem Int Ed Engl. 2017 Mar 27;56(14):3997-4001. doi: 10.1002/anie.201700290. Epub 2017 Mar 2.

Authors

Marion Daniel¹, Guillaume Dagousset¹, Patrick Diter¹, Pierre-André Klein², Béatrice Tuccio², Anne-Marie Goncalves¹, Géraldine Masson³, Emmanuel Magnier¹

Affiliations

¹ Institut Lavoisier de Versailles, UMR 8180, Université de Versailles-Saint-Quentin, 78035, Versailles Cedex, France.
² Aix-Marseille Université-CNRS, Institut de Chimie Radicalaire, UMR 7273, 13397, Marseille Cedex 20, France.
³ Institut de Chimie des Substances Naturelles, CNRS, 91198, Gif-sur-Yvette Cedex, France.

PMID: 28252241
DOI: 10.1002/anie.201700290

Abstract

Reported herein is the use of S-perfluoroalkyl sulfilimino iminiums as a new source of R_F radicals under visible-light photoredox catalysis (R_F =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.

Keywords: EPR spectroscopy; fluoroalkylation; photochemistry; radicals; reaction mechanisms.

Publication types

Research Support, Non-U.S. Gov't