Hetaryl Thioketones: Synthesis and Selected Reactions

Abstract

ABSTRACT A series of phenyl/hetaryl and bishetaryl thioketones have been prepared via oxygen/sulfur exchange of the corresponding ketones by treatment with Lawesson's reagent. The nonsymmetrical ketones were conveniently accessible via the reactions of lithiated furan, thiophene, and selenophene with N , N ‐dimethylbenzamide and hetarylcarboxamides, respectively, whereas the symmetrical ketones were obtained by treatment of ethyl N , N ‐dimethylcarbamate with 2 equiv of lithiated heterocycles. Under typical conditions, selected examples of the hetaryl thioketones were oxidized selectively to give thiocarbonyl S ‐oxides (sulfines). Reactions with diazomethane at –65°C yielded 1,3‐dithiolanes in a regioselective manner and hetero‐Diels–Alder reactions of 2‐thienyl substituted thioketones with dimethyl acetylenedicarboxylate yielded the corresponding 7 H ‐thieno[2,3‐ c ]thiopyran‐4,5‐dicarboxylates.