Fluoro groups on pyridines facilitate nucleophilic aromatic substitutions while providing convenient spectroscopic handles for ¹⁹F NMR kinetic analysis. Investigations of a pharmaceutically important pyrrolopyridine cyclization highlight a number of surprising mechanistic details. The reaction proceeds via an LDA deprotonation of 2-fluoro-3-methylpyridine followed by nucleophilic addition to benzonitrile and subsequent intramolecular Chichibabin cyclization. The resting state of the reaction before nitrile addition is a 1,4-N-lithiodihydropyridine dimer. Quenching the dimer with water gives a quantitative yield of 1,4-dihydropyridine and rearomatized 1,4-pyridine. The rate of LDA deprotonation has been shown to be first order in fluoromethylpyridine, third order in THF, and half-order in LDA.