Ruthenaelectro‐Catalyzed Domino Three‐Component Alkyne Annulation for Expedient Isoquinoline Assembly

The electrochemical three‐component assembly of isoquinolines has been accomplished by ruthenaelectro‐catalyzed C−H/N−H functionalization. The robustness of the electrocatalysis was reflected by an ample substrate scope, an efficient electrooxidation, and an operationally friendly procedure. The isolation of key intermediates and detailed mechanistic studies, including unprecedented cyclovoltammetric analysis of a seven‐membered ruthenacycle, provided support for an unusual ruthenium(II/III/I) regime.