Photogenerated azaxylylenes undergo intramolecular cycloadditions to 1,3,4-oxadiazole pendants, which are accompanied by concomitant release of dinitrogen, yielding functionalized ketopiperazinoquinolinols containing an oxirane moiety fused to the quinolinole moiety while spiro-connected to diketopiperazine. These primary photoproducts are reactive versatile intermediates which can be further d...