Abstract
A series of (cyclo)aliphatic thioketones have been tested towards trifluoroacetonitrile imines, generated in situ via base-induced dehydrohalogenation of the respective hydrazonoyl bromides. Typically, non-enolisable thioketones yielded exclusively 3-trifluromethyl-2,3-dihydro-1,3,4-thiadiazoles as a result of completely regio-, chemo-, and diastereoselective (3+2)-cycloaddition. In the case of 2,2,4,4-tetramethylcyclobutane-1,3-dithione a competitive rearrangement followed by trapping of title 1,3-dipole by the C=S group of the initially formed β-dithiolactone was observed. Enolizable (1R)-thiocamphor also provided the expected (3+2)-cycloadducts along with the insertion products found in a ratio reflecting electronic properties of the nitrile imine. The latter results indicate remarkable electrophilic nature of the electron-deficient fluorinated nitrile imines, and implies a possible step-wise mechanism of the studied reaction.
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