A catalyst-free one-pot methodology that enables direct nitrogen interception of chitosan/chitin for imidazo[1,5-a]pyridines was developed. This strategy features direct synthesis of important deuterated imidazo[1,5-a]pyridines and tridentate ligands. In particular, a broad group of previously inaccessible products including saturated 1-alkylimidazo[1,5-a]pyridines are unprecedently synthesized by this protocol.