“Naked Nickel”‐Catalyzed Heteroaryl‐Heteroaryl Suzuki–Miyaura Coupling

In this article we report that the air‐stable “naked nickel” [Ni(4‐CF3stb)3] is a competent catalyst in the catalytic Suzuki‐Miyaura cross‐coupling reaction (SMC) between heteroaryl bromides and heteroaromatic boron‐based nucleophiles. The catalytic system is characterized by its ability to avoid decomposition or deactivation in the presence of multiple Lewis‐basic sites. The protocol permits the formation of C‒C bonds between two heteroaryl moieties in the absence of complex exogenous ligands, thus minimizing screening procedures and simplifying reaction setups. This method accommodates combinations of distinct 6‐membered heteroaryl bromides and 5‐ and 6‐membered heterocyclic B‐based nucleophiles.