In the presence of a catalytic amount of Cp*RuCl(cod), 1,6-diynes were allowed to react chemo-and regioselectively with electron-deficient nitriles and heterocumulenes at 60-90 degreesC to afford heterocyclic compounds. The mechanism of the ruthenium-catalyzed regioselective formations of bicyclic pyridines and pyridones were analyzed on the basis of density functional calculations. Cyclocotrimerizations of ethyl propiolate with ethyl cyanoformate or propyl isocyanate gave rise to two of the four possible pyridine or pyridone regioisomers.