Anionic Bisoxazoline Ligands Enable Copper‐Catalyzed Asymmetric Radical Azidation of Acrylamides

Abstract Asymmetric radical azidation for the synthesis of chiral alkylazides remains a tremendous challenge in organic synthesis. We report here an unprecedented highly enantioselective radical azidation of acrylamides catalyzed by 1 mol % of a copper catalyst. The substrates were converted to the corresponding alkylazides in high yield with good‐to‐excellent enantioselectivity. Notably, employing an anionic cyano‐bisoxazoline (CN‐Box) ligand is crucial to generate a monomeric Cu II azide species, rather than a dimeric Cu II azide intermediate, for this highly enantioselective radical azidation.