Whereas 2,3-dichloropyridine and 2,5-dichloro-4-(lithiooxy)pyridine undergo deprotonation exclusively at the 4- and 2-positions, resp., optional site selectivity can be implemented with 2,5- and 3,4-dichloropyridine (which are attacked, depending on the choice of the reagents, at either the 4- or 6- and either the 2- or 5-positions, resp.). Upon treatment with lithium diisopropylamide, 2,4-dichloro-3-iodopyridine, 3,5-dichloro-4-bromopyridine, and 2,6-dichloro-3-iodopyridine afford 5-, 2-, and 4-lithiated intermediates, but the latter isomerize instantaneously to species in which lithium and iodine have swapped places, the driving force being the low basicity of C-Li bonds when flanked by two neighboring halogens. [on SciFinder (R)]