This work describes an environmentally friendly method for the synthesis of benzoxazinones, quinoxalinones and benzothiazoles by the reaction of α-arylglyoxylic acids and ortho-functionalized aniline. In this reaction, no other reagents are needed except for reactants and solvents. The reaction was carried out at a mild temperature of 50 °C with only water and/or carbon dioxide as the by-product. Therefore, the reaction has high practical atom economy. In addition, this strategy could be scaled up to the gram level, and the natural product Cephamandole A could be synthesized on a mass scale.