Photoelectrochemical Iron(III) Catalysis for Late-Stage C─H Fluoroalkylations.

Chemo- and site-selective functionalization of complex molecules poses a fundamental challenge. Herein, we introduce a resource-economic photoelectrocatalysis strategy to enable versatile direct fluoroalkylations catalyzed by Earth-abundant iron and paired with the hydrogen evolution reaction (HER). Notably, the devised approach proved amenable to versatile late-stage C─H fluoroalkylations of bio-relevant heterocycles, such as xanthines, nucleobases, and nucleosides. Mechanistic studies supported a ligand-to-metal charge transfer-induced formation of the fluoroalkyl radical.