A Shelf‐Stable Reagent for Photocatalytic Radical Pentafluorosulfanylation of Styrene Derivatives

Abstract We have developed the first family of air‐ and moisture‐stable pentafluorosulfanylation (SF₅) reagents. Although the SF₅ group is a bioisostere of the trifluoromethyl group (CF₃)—exhibiting even greater electronegativity and lipophilicity, attributes that have earned it the nickname “super trifluoromethyl group”—the development of shelf‐stable, non‐toxic, and easy‐to‐handle SF₅‐incorporating reagents had remained elusive for over 70 years since its discovery. Our discovery enables the synthesis of per‐ and polyfluoroalkyl substances (PFAS)‐free fluorinated compounds, offering significant advantages over traditional CF₃ analogs. These new reagents exhibit promising reactivity under photochemical conditions, efficiently facilitating the formation of novel SF₅‐containing molecules. Moreover, our approach is compatible with the late‐stage functionalization of complex molecules. Mechanistic studies have provided valuable insights into the underlying reaction pathways.