Redox-Paired Activation of Sulfur Hexafluoride Enables Nucleophilic C(sp3)–F Bond Formation
Year: 2026
Type: preprint
Abstract: Sulfur hexafluoride (SF6) is a potent greenhouse gas whose direct use as a fluorine source in organic synthesis remains underdeveloped. Here, we disclose complementary photoredox and electrochemical strategies for nucleophilic fluorinations with SF6, merging oxidative formation of carbocation intermediated from alkoxamines, carboxylic acids, or thiols with SF6 reduction, the latter providing fluoride for C(sp3)–F bond formation. The photochemical protocol efficiently converts electronrich substrates and tolerates a broad range of functional groups, whereas paired electrolysis extends the reaction to electronically deactivated substrates. Together, the two methods enable fluorination of diverse benzylic and aliphatic substrates, including late-stage fluorination of structurally complex derivatives of pharmaceuticals, natural products, and agrochemicals.
Source: ChemRxiv
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Funder: Deutsche Forschungsgemeinschaft
OpenAlex ID: W7215100018