Copper(II)‐Catalyzed Synthesis of Quinoxalines From <i>β</i> ‐Alkyl Nitroolefins and <i>o</i> ‐Phenylenediamines

A novel copper‐catalyzed protocol is discovered for the synthesis of quinoxalines through the direct coupling of β , β ‐disubstituted nitroalkenes and o ‐phenylenediamines. The cascade transformation proceeds via a mechanistically intriguing pathway involving allylic CH bond oxidation followed by cyclocondensation. Remarkably, o ‐phenylenediamines are proposed to play a dual role, serving not only as conventional condensation partners but also as essential ligands that facilitate the copper‐catalyzed oxidative transformation.