Efficient and Versatile Buchwald–Hartwig Amination of (Hetero)aryl Chlorides Using the Pd–PEPPSI‐IPr(NMe2)2 Precatalyst in the Presence of Carbonate Base

Abstract

AbstractThe 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.