Radical Anion-Driven, Photocatalyst-Free α-Aminoalkylation of Quinoxalin-2(1 H )-ones

Abstract Radical C–H functionalization at the α-position of amines has intrigued organic chemists for decades. To overcome the requirement for harsh conditions, our strategy involves the 1,5-HAT process to efficiently generate the α-aminoalkyl radical. The reaction is promoted by the formate anion, a single electron reductant, and shows a wide range of compatibility with various quinoxalin-2(1H)-one derivatives and amines. Mechanistic investigations and DFT calculations reveal that the intermediate from radical addition shows a strong reducing ability to propagate the C–H functionalization without the need for a photocatalyst.