Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex

We report the development of a new
aminoxyl radical catalyst, CHAMPO,
for the electrochemical diazidation of alkenes. Mediated by an anodically
generated charge-transfer complex in the form of CHAMPO–N3, radical diazidation was achieved across a broad scope of
alkenes without the need for a transition metal catalyst or a chemical
oxidant. Mechanistic data support a dual catalytic role for the aminoxyl
serving as both a single-electron oxidant and a radical group transfer
agent.