"Naked Nickel"-Catalyzed Amination of Heteroaryl Bromides.

In this Letter, we report that the air-stable "naked nickel" [Ni(4-tBustb)3] is a competent catalyst in thermal C-N bond formation between (hetero)aryl bromides and N-based nucleophiles. The catalytic system is characterized by a "naked nickel" complex and Zn and by the absence of external light sources, photocatalysts, exogenous ligands, and electrical setups. Upon application of this method, various heteroaryls bearing Lewis-basic heteroatoms can be accommodated and directly aminated with a set of primary and secondary amines.