Rerouting nucleophilic substitution from the 4-position to the 2-or 6-position of 2,4-dihalopyridines and 2,4,6-trihalopyridines: The solution to a long-standing problem

2,4-Difluoro-, 2,4,6-trifluoro-, and 2,3,4,6-tetrafluoropyridine undergo nucleophilic substitution preferentially if not exclusively at the 4-position. However, after the introduction of a trialkylsilyl group at C-3 or C-5, the halogen at the 6-(2-)position is displaced selectively. This synthetically valuable regiocontrol can also be realized with other halopyridines such as 2,4-dichloro- and 2,4,6-trichloropyridine.