Electro‐oxidative methylation of 2‐isocyanobiaryls using N,N‐dimethylformamide (DMF) as carbon source: Synthesis of 6‐methylphenanthridines

A benign electrochemical method to access 6‐methylphenanthridines from 2‐isocyanobiaryls using N,N‐dimethylformamide (DMF) as a methyl source is reported. The protocol operates at ambient temperature without the need for harmful methylating reagents. Mechanistic studies suggested that DMF delivered a methylene synthon, followed by reduction at the cathode and tautomerization. The method offers environmental benefits by avoiding metal‐based reagents and harsh conditions.