Electricity-Induced Radical 7- <i>endo</i> -Cyclization from Aryldiazonium Salts: Synthesis of Trifluoromethylated Azepines

Nitrogen-containing heterocycles represent pivotal structural motifs that pervade diverse pharmaceuticals and bioactive agents. Arenediazonium salts function as versatile building blocks for the synthesis of such heterocycles while preserving the N₂ moiety. Herein, we report an electrochemical strategy that facilitates the efficient assembly of structurally complex, multi-heteroatom heterocyclic systems, enabling the simultaneous formation of C═N bonds and construction of seven-membered rings, from trifluoromethanesulfinates and aryl diazonium salts. The design of this reaction was guided by the principles underlying radical polarity matching and a sustainable synthesis. This mild, electrochemically triggered radical process provides an atom-economical pathway to a diverse range of fluorinated seven-membered <i>N</i>-heterocycles, obviating the need for stoichiometric oxidants.