1.10 The Pentafluorosulfanyl Group (SF5)

Abstract The pentafluorosulfanyl group imparts exceptional thermal, chemical, and metabolic stability to organic scaffolds. Despite being first described seven decades ago, it remains an under-utilized motif in organofluorine chemistry, primarily due to a lack of efficient synthetic routes that proceed under mild reaction conditions. Nonetheless, the renewed interest in pentafluorosulfanyl scaffolds over the last decade has enabled the preparation of important pentafluorosulfanyl building blocks. Herein, the major synthetic strategies for the preparation of pentafluoro-λ6-sulfanyl-containing compounds are reviewed, including the synthesis of (pentafluorosulfanyl)arenes via oxidative halogenation and the direct pentafluorosulfanylation of aliphatic cores, achieved mainly using pentafluorosulfanyl chloride as a reagent.