Making the SF 5 Group More Accessible: A Gas‐Reagent‐Free Approach to Aryl Tetrafluoro‐λ 6 ‐sulfanyl Chlorides

Modern pentafluorosulfanyl (SF 5 ) chemistry has an Achilles heel: synthetic accessibility. Herein, we present the first approach to aryl‐SF 4 Cl compounds (key intermediates in state‐of‐the‐art aryl‐SF 5 synthesis) that overcomes the reliance on hazardous fluorinating reagents and/or gas reagents (e.g. Cl 2 ) by employing easy‐to‐handle trichloroisocyanuric acid, potassium fluoride, and catalytic amounts of acid. These simple, mild conditions allow direct access to aryl‐SF 4 Cl intermediates that either have not been or cannot be demonstrated using previous methods. Furthermore, the same approach provides access to aryl‐SF 3 and aryl‐SeF 3 compounds, which extend the applications of this chemistry beyond arene SF 5 ‐functionalization, and demonstrate its ability to address a more general oxidative fluorination problem.