5‐aminothiazolium salts as potential cyclic azomethine ylides: Base‐induced cycloaddition reactions with aryl,alkyl, and benzoyl isothiocyanates

Reactions of the in situ generated thiazoles 2 with aryl and alkyl isothiocyanates appear to be totally regioselective and give the unexpected 5‐(phenylthio)imidazolium‐4‐thiolates 3 . Such rapid interconversion of mesoionic compounds is explained by a 1,3‐dipolar addition to the C=N bond of the heterocumulene followed by tBuNCS elimination. Similar interactions with benzoyl isothiocyanate exclusively proceed on the C=S unsaturation of the heteroallene moiety and produce the 4‐(phenylthio)thiazolium‐5‐amidines 12 . Structural assignment of isolated imidazoles and thiazoles is based on ¹³C NMR data and chemically confirmed by the NaBH₄ reduction of the alkylated derivatives 5 and 13 . Efforts to isomerize the starting mesoionic thiazole 2a without the use of tBuNCS are unsuccessful. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 10:16–26, 2000