The influence of substituents at C-3 of 2, 4-dichloropyridines on their reactivity and regioselectivity in Pd-catalyzed cross-couplings is studied. As a model reaction, the (Ph3P) 2PdCl2-catalyzed Stille coupling between 2-furyl (tributyl) tin and pyridines is chosen. Increased electron-withdrawing ability of a substituent at the pyridine 3-position improves the overall reactivity. Absolute selectivity for coupling at C-2 is achieved with an amino ...