Electro‐Redox‐Mediated Formal (3+2) Cycloaddition: Sustainable Synthesis of Tetrazoloquinoxalinones

A sustainable electrochemical protocol for the synthesis of tetrazolo[1,5‐ a ]quinoxalin‐4(5 H )‐one is developed. The notable feature of this method is the application of an electro‐redox mediator 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ), which empowered the use of sodium azide as an economical azide source. The developed formal (3 + 2) cycloaddition strategy affords a broad range of functionalized tetrazoloquinoxalinone derivatives with potential biological relevance. Detailed synthetic and electrochemical studies elucidated the mediator‐assisted electrocatalytic mechanism, highlighting the advantages of this transition metal‐free electrochemical approach.