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.