Treatment of 2,6-difluoropyridine with lithium diisopropylamide in THF solution at -78 degrees C effects ortholithiation quantitatively. Warming the solution to 0 degrees C converts the aryllithium to 2-fluoro-6-(diisopropylamino)pyridine. Rate studies reveal evidence of a reversal of the ortholithiation and a subsequent 1,2-addition via two monomer-based pathways of stoichiometries [ArH center dot i-Pr2NLi(THF)]double dagger and [ArH center dot iPr(2)NLi(THF)(3)]double dagger. Computational studies fill in the structural details and provide evidence of a direct substitution without the intermediacy of a Meisenheimer complex.