Selective amidation by a photocatalyzed umpolung reaction

A metal-catalyzed organic transformation merged with another organophotocatalyst has been developed under mild conditions for production of α-ketoamides. CuI-catalyzed highly selective and rapid COCH2-amidation in the presence of electrophilic CαO bonds, which is synchronized by an eosin Y (EY)-photocatalyst, furnishes a wide range of labile α-ketoamides, unsymmetrical oxalamides and chiral analogues on the treatment of 1,3-dicarbonyls with amines, PhIO and LED light at room temperature. The current strategy opens up a new avenue to making photocatalysis a common synthetic tool for large-scale production in academia and industry.