Oxidative Amidation of α-TEMPO-Aryloylnitromethane Adducts and Anilines: A Direct Synthesis of α-Ketoamides

We report an oxidative amidation of α-TEMPO-aryloylnitromethane adducts, prepared in one step from aryloylnitromethanes and TEMPO, with anilines to give α-ketoamides. The reaction proceeds at room temperature within short reaction times, offering a practical method for accessing this important class of compounds. A variety of α-ketoamides-valuable building blocks in organic synthesis and privileged pharmacophores in medicinal chemistry were obtained in yields up to 86%, with broad tolerance for common functional groups. Reduced efficiency is observed with anilines bearing bulky or strongly electron-withdrawing substituents. Preliminary mechanistic data (HR-MS and Griess test) suggest that multiple pathways may be operative, all converging on the generation of nitrite species. While additional TEMPO seems beneficial for most substrates, its role is not universally required and remains a point of mechanistic interest for further study. This work highlights a mild and operationally simple strategy for the preparation of structurally diverse α-ketoamides.