AbstractCatalytic systems combining ortho‐(dimesitylboryl)phenylphosphines and palladium precursors have been evaluated in the Suzuki–Miyaura couplings of chloro‐N‐heterocycles, in particular 2‐chloropyridines, with arylboronic acids. The Lewis basic character of the substrates does not interfere with the Lewis acidic site of the ligands, even for a substrate featuring free NH2 groups. The influence of several reaction parameters has been studied and the ortho‐dimesitylboryl moiety was actually found to substantially enhance the catalytic performance. The role of this group has been examined using preformed phosphine‐borane/Pd complexes and the formation of an original phosphine/η4‐boratabutadiene complex has been identified as a possible deactivation pathway. Regioselective coupling of 2,6‐dichloro‐3‐nitropyridine with phosphine‐borane/Pd catalysts has also been explored, and sequential double cross‐couplings were found to give a direct and efficient access to unsymmetrical 2,6‐diarylpyridines.magnified image