Synthesis of Indoles via Electron-Catalyzed Intramolecular C-N Bond Formation.

A new protocol for the preparation of N-substituted indole-3-carboxylates has been developed. The key C-N bond formation occurs under transition-metal-free conditions employing a t-BuOK/DMF system without special initiators or additives. Across a number of substrates, indoles were afforded in yields higher or comparable to those obtained under transition-metal-catalyzed conditions. While demonstrating high functional group tolerance, new conditions are particularly attractive for manufacturing halogenated indoles that cannot be made in a pure form using other metal-based catalytic methods.