Using the Thiyl Radical for Aliphatic Hydrogen‐Atom Transfer: Thiolation of Unactivated C−H Bonds

Abstract A metal‐ and catalyst‐free thiyl‐radical‐mediated activation of alkanes is described. Tetrafluoropyridinyl disulfide is used to perform thiolation of the C−H bonds under irradiation with 400 nm light‐emitting diodes. The key C−H activation step is believed to proceed via hydrogen‐atom abstraction effected by the fluorinated thiyl radical. Secondary, tertiary, and heteroatom‐substituted C−H bonds can be involved in the thiolation reaction. The resulting sulfides have wide potential as photoredox‐active radical precursors in reactions with alkenes and heteroarenes.