Formal Radical Deoxyfluorination of Oxalate‐Activated Alcohols Triggered by the Selectfluor‐DMAP Charge‐Transfer Complex

We present a photon‐ and metal‐free approach for the radical fluorination of aliphatic oxalate‐activated alcohols. The method relies on the spontaneous generation of the N‐(chloromethyl)triethylenediamine radical dication, a potent single electron oxidant, from Selectfluor and 4‐(dimethylamino)pyridine. The protocol is easily scalable and provides the desired fluorinated products within only a few minutes reaction time.