Separation of Redox Events Unlocks Electrocatalytic C–N Bond Formation with Inert Fluoroarenes

Nucleophilic aromatic substitution (SNAr) reactions are a critical method for forming C–N bonds in synthetic campaigns, but limitations in electrophile electronics restrict access to a large portion of chemical space. Photochemical oxidation of fluoroarenes offers limited success due to back-electron transfer to solution-phase reduced photocatalysts. Herein, we describe an electrochemical strategy to overcome this obstacle by spatially separating redox events at electrode surfaces, extending the lifetime of the activated electrophile. Through stabilization of oxidized product using voltage control and HFIP solvent, we establish that the reaction proceeds with catalytic charge via a proposed uphill redox chain mechanism. A wide range of electron-rich fluoroarenes and azoles are tolerated, and the redox catalytic nature of this e-SNAr reaction allows for a high degree of scalability