Electrolyte‐Free Electrochemical C3‐Arylmethylation of Indoles with Tertiary/Secondary N‐Methyl Anilines using N‐Methyl as the Methylene Source

An electrochemical approach devoid of electrolytes, oxidants, metals, and light is established for the C3‐arylmethylation of indoles using tertiary/secondary N ‐methyl anilines, demonstrating a wide substrate scope, with N ‐methyl serving as the methylene donor. Mechanistic investigations indicate that the presumed C3‐aminomethylated indole acts as a reactive intermediate, facilitating the formation of the arylmethylated product via radical/electrophilic addition, anodic oxidation/deprotonation, fragmentation, and cathodic reduction/protonation processes.