Cascade Rearrangement: Nitro Group-Participating Syntheses of 1,2,5-Thiadiazoles and 1,2,4-Thiadiazolones.

Abstract

A trifluoroacetic anhydride-mediated cascade process for the synthesis of thiadiazole derivatives is described. 1,2,5-Thiadiazoles and 1,2,4-thiadiazolones could be obtained by variation of the reaction conditions. A group of functionalized thiadiazole derivatives were synthesized in moderate to good yields from nitro-group-containing N-tert-butanesulfinamides. The reactions involved in this tandem process are a Pummerer-like rearrangement of the tert-butanesulfinamide unit, a nitrile oxide formation via nitro group rearrangement, addition of oxygenated nucleophiles, and an N-S bond forming cyclization followed by concomitant elimination.