The one-pot de novo synthesis of pentasubstituted pyridines was realized following the process of Au(I)-autotandem catalysis and subsequent aromatization. The process involves aza-enyne metathesis with aryl propiolates to yield 1-azabutadienes and their addition/6π-electrocyclization sequence with the other propiolate units. The resultant 1,4-dihydropyridines were aromatized to furnish the pyridines in the presence of atmospheric oxygen. The aryl propiolates were regioselectively incorporated into the ring system to afford 2-arylpyridines as the sole product.