Abstract The well-defined [Pd (IPr*)(cinnamyl) Cl] complex is reported as one of the best N- heterocyclic carbene (NHC)-based pre-catalysts for the Buchwald–Hartwig amination reaction. This catalytic system displays high efficiency for the coupling of numerous (hetero) aryl chlorides, with a wide range of amines, at room temperature or at extremely low catalyst loading (as low as 0.025 mol%).