Bench-stable reagents for modular access to persulfuranyl scaffolds

Pentafluorosulfanyl group has been long considered a potential (bio)isostere for tert-butyl and trifluoromethyl groups, yet limitations in methodologies have constrained access to it. To bridge this gap, we have developed a general pentafluorosulfanylation platform that employs bench-stable solid reagents to generate SF₅ radicals via a decarboxylation and β-scission sequence. This strategy enables a variety of operationally simple transformations, expanding the accessibility of SF₅-containing molecules. Notably, this reagent design is also adaptable to other persulfuranyl groups, such as trifluoromethyl tetrafluorosulfanyl and aryl tetrafluorosulfanyl groups. Taken together, generating a collection of these stable reagents and practitioner-friendly chemical methodologies enables the synthesis of challenging and biologically relevant sulfur(VI) chemical entities in an expedient manner.