Photoelectrochemical iron(III)-catalysis for late-stage C–H fluoroalkylations

Chemo- and site-selective functionalization of complex molecules poses a fundamental challenge. In this regard, the synergetic combination of photoexcitation with electron transfer by anodic oxidation bears unique potential for novel reaction manifolds that go beyond individual photo- or electrochemistry. ^1–3 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.