Recent Progress in Coupling of Two Heteroarenes

The biheteroaryl structural motif is prevalent in polymers, advanced materials, liquid crystals, ligands, molecules of medicinal interest, and natural products. Many types of synthetic transformations have been known for the construction of heteroaryl–heteroaryl linkages. Coupling reactions provide one of the most efficient ways to achieve these biheterocyclic structures. In this review, four types of coupling reactions are discussed: 1) transition‐metal‐catalyzed coupling reactions of heteroaryl halides or surrogates with heteroarylmetals; 2) direct inter‐ and intramolecular heteroarylations of C sp 2H bonds of heteroarenes with heteroaryl halides or pseudohalides; 3) oxidative CH/CH homo‐ and cross‐couplings of two unpreactivated heteroarenes; and 4) transition‐metal‐catalyzed decarboxylative cross‐coupling reactions between haloheteroarenes or heteroarenes and heteroarenecarboxylic acids. The general purpose of this review is to give an exhaustive and clear picture in heteroaryl–heteroaryl bond formation as well as its application in the synthesis of natural products, pharmaceuticals, catalyst ligands, and materials. Opposites attract: The biheteroaryl structural motif is prevalent in polymers, advanced materials, molecules of medicinal interest, and natural products. In this article, four types of coupling reactions are reviewed. The general purpose of this review is to give a clear picture in heteroaryl–heteroaryl bond formation as well as its application in the synthesis of natural products, pharmaceuticals, catalyst ligands, and materials.