Synthesis of Biheteroaryls by Pd-Catalyzed Homocoupling of Heteroaryl Bromides.

Symmetrical biheteroaryl compounds, such as bypyridines and bipyrazoles, are important ligands in transition-metal catalysis. They also serve as synthetic precursors of photo catalysts/sensitizers, bioactive agents, and energetic materials. To facilitate the concise synthesis of these useful structures, an efficient Pd-catalyzed homocoupling of heteroaryl bromides has been successfully established using the electron-rich and sterically hindered monophosphorus ligand BIDIME. The coupling protocol features a tandem Miyaura borylation/Suzuki coupling sequence and exhibits unprecedented tolerance of a wide range of heteroaryl bromides, providing a series of symmetrical biheteroaryls in moderate to good yields. Notably, the use of the corresponding polymeric ligand, PolyBIDIME, enabled the recycling of a palladium catalyst, demonstrating the potential of the homocoupling in practical applications.