Abstract Tri-and tetrasubstituted ortho-bromobiaryls have been synthesized in good-to- excellent yields by aryne cross-coupling reactions starting from 1, 3-dimethoxybenzene and functionalized 1, 2-dibromobenzenes. This study outlines the influence of the 1, 2- dibromobenzene precursor as well as the reaction temperature on the outcome of the aryl– aryl bond formation and indicates, in the case of dissymmetrical benzyne precursors, how ...