Kimberly Benedetti Vega, Alejandro Heredero Sánchez, Tanumoy Mandal, Wagner Silva, Ruth M. Gschwind, Attilio C. Neto, Marco A. B. Ferreira, Burkhard Koenig, Márcio W. Paixão
High Resolution Image Download MS PowerPoint Slide Herein, we report a photocatalytic method for the selective functionalization of α-C(sp 3 )-H bonds adjacent to the nitrogen atom in amides. By harnessing a synergistic combination of hydrogen atom transfer (HAT), consecutive photoinduced electron transfer (ConPET), and reductive radical-polar crossover, we efficiently incorporated high-value electrophiles, including CO 2, 13 CO 2, and deuterium, at the α- N position. The transformation proceeds in moderate to high yields across a diverse range of amides, representing a significant advancement in both isotopically labeled α-amino acid synthesis and amide deuteration.