The precatalyst Pd-PEPPSI-IPr(NMe2)2, in which the IPr ligand was modified by attachment of two dimethylamino groups on to the 4- and 5-positions of the imidazolyl heterocycle, was found to show high catalytic efficiency in the Buchwald-Hartwig amination under mild conditions using Cs2CO3 as a weak base, using a low catalyst loading of 1 mol-%. The protocol is applicable to aryl chlorides bearing base-sensitive substituents, as exemplified by the coupling of 4-chloroacetophenone with aniline. It can also be used with an unprecedentedly wide range of amines, including strongly basic secondary alkylamines, primary arylamines, and primary alkylamines.