Abstract The palladium-catalyzed β-arylation of ester enolates with aryl bromides was studied both experimentally and computationally. First, the effect of the ligand on the selectivity of the α/β-arylation reactions of ortho-and meta-fluorobromobenzene was described. Selective β-arylation was observed for the reaction of o-fluorobromobenzene with a range of biarylphosphine ligands, whereas α-arylation was predominantly observed with ...