Unexpected Oxidative Ring Opening of Electron-Rich 3‑Aminobenzofurans into α‑Ketoimines Derivatives

An unexpected ring opening of 3-aminobenzofurans promoted by NaOtBu in hot toluene, leading to a variety of α-ketoimines, is described. In the presence of 3-iodobenzofurans, NaOtBu mediates the 3-amino­benzo­furans ring opening via a possible radical pathway without the help of any external radical sources.