Electrochemically Enabled Chemodivergent Azidohydroxylation and Diazidation of Trifluoromethylalkenes with Trimethylsilyl Azide

A facile and straightforward electrochemical oxidative azidohydroxylation and diazidation of α-CF₃ alkenes with TMSN₃ has been achieved. Significantly, a series of densely functionalized and potentially medicinally valuable β-trifluoromethylated azido compounds were assembled under mild conditions using a constant current in an undivided cell and without using any external oxidants and catalysts. Notably, this protocol exhibited a broad scope and functional group tolerance to deliver azidohydroxyla-tion and diazidation products, respectively, by replacing the electrode and the solvent. The reaction mechanism was also preliminarily studied.