An intramolecular formal metal-free intramolecular [2 + 2 + 2] cycloaddition for the formation of pyridines has been investigated with M06-2X and B3LYP density functional methods, and compared to the experimentally established three-step mechanism that involves ene reaction-Diels-Alder reaction-hydrogen transfer. The ene reaction of two alkynes is the rate-determining step. This is considerably easier than other possible mechanisms, such as those involving an ene reaction of an alkyne with a nitrile, a one-step [2 + 2 + 2] cycloaddition, or a 1,4-diradical mechanism. The relative facilities of these processes are analyzed with the distortion-interaction model. A bimolecular hydrogen-transfer mechanism involving a radical-pair intermediate is proposed rather than a concerted intramolecular 1,5-hydrogen shift for the last step in the mechanism.