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An effective copper-catalyzed direct C–H/N–H cross-coupling of quinoxalin-2(1H)-ones with diverse unprotected 2-quinoxalinones and 2-quinolinones has been developed. This protocol provides a convenient route, with broad substrate scope, good functional group tolerance, and high atom economy, to various important quinoxalin-2(1H)-one-containing biheteroaryls, which are privileged structures in many biologically active compounds.

Graphical abstract: Copper-catalyzed C–H/N–H cross-coupling reactions for the synthesis of 3-heteroaryl quinoxalin-2(1H)-ones

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