Synthesis and reactivity of tetrahydroimidazo [1,5-b][1,2,4]oxadiazol-2(1H)-thiones

Abstract

1,3-Dipolar cycloaddition of imidazoline 3-oxides I with methylisothiocyanate proceeds regio- and diastereoselectively to give tetrahydroimidazo[1,5-b][1,2,4]oxadiazol-2(1H)-thiones 3 in high yields. The cis configuration of the adducts was proved by our double cis elimination test as well as by NOESY experiments. Adducts 3a-c undergo ring opening at reflux in acetonitrile to give imidazoles while 3d-e undergo retro dipolar cycloaddition to give the starting nitrones 1d-e. The imidazooxadiazol-2-thiones 3a-e were treated with concentrated HCl in ethanol at 50degreesC to give the corresponding 4H-[1,2,4]oxadiazole-5-thione only in cases in which the substituent at C-6 is an aryl.