Lithiation of N-(pyridin-3-ylmethyl)pivalamide, tert-butyl N-(pyridin-3-ylmethyl)carbamate and N'-(pyridin-3-ylmethyl)-N,N-dimethylurea with three mole equivalents of t‑butyllithium in anhydrous THF at -78 °C takes place on the nitrogen and on the ring at the 4-position. The dilithium reagents thus obtained react with various electrophiles to give the corresponding substituted derivatives in high yields. On the other hand, regioselective side-chain lithiation occurs with LDA (3.3 mole equivalents) at -20 to 0 °C.