Photoredox‐Catalyzed Selective Dioxygenation of <i>gem</i>‐Difluorocyclopropanes to Generate α,α‐Difluorinated‐1,3‐diethers

Abstract gem ‐Difluorocyclopropanes are valuable synthetic intermediates in organofluorine chemistry; however, their reactivity often involves intermediates prone to fluorine elimination, leading to monofluorinated products. Here, we present a photoredox‐catalyzed dioxygenation of gem ‐difluorocyclopropanes with alcohols, which retains both fluorine atoms and yields α,α‐difluorinated‐1,3‐diethers. This method is operationally simple, employs inexpensive and standard reagents, and demonstrates broad functional group tolerance. The reaction is scalable, enabling the use of the gem‐difluorocyclopropane motif as a masked precursor for α,α‐difluorinated‐1,3‐diethers in synthetic sequences. Preliminary mechanistic studies suggest a radical‐mediated process involving concerted S N 2‐like ring‐opening functionalization.