A new photoredox-active group was applied for the generation of fluorinated radicals from difluorostyrenes under blue light irradiation.

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.

A visible-light-promoted fluoroalkylation-thiolation of alkenes is described. 4-Tetrafluoropyridinylthio fragment serves as a photoredox-active group in the initiation step and undergoes radical group transfer important for the reaction efficiency. In the...