Direct Electrooxidative Selenylamination of Alkynes: Access to 3‐Selenylindoles

Abstract A novel metal‐ and oxidant‐free electrooxidative selenylamination of o ‐aminophenacetylenes with diselenides for achieving 3‐selenylindoles has been developed with moderate to excellent yield. The reaction proceeded smoothly with a broad substrate scope and highly functional group tolerance. The synthetic practicality of this innovative approach was demonstrated by its easy scalability. Moreover, mechanistic studies revealed that an in‐situ generated selenium cation might be the key intermediate for the electrochemical selenocyclization process.