Regiospecific net 1, 7-cycloaddition reactions of electron-rich or strained olefins and electron-donor acetylenes occur readily (-70 to-10 “C) with diazoazoles having nitrogen in the 2-positions of their azole rings. Diazoazoles such as 5-tert-butyl-3-diazo-3H-pyrazole (20), 3-diazo-5-phenyl-3H-pyrazole (24), 2-diazo-2H-imidazole (28), 4, 5-dicyano-2-diazo- 2H-imidazole (12), 4-diazo-4H-imidazole (63), 4-diazo-5-phenyl-4H-l, 2, 3-triazole(70), 5- ...