Hetero-Diels–Alder reactions of hetaryl and aryl thioketones with acetylenic dienophiles

Abstract

Selected hetaryl and aryl thioketones react with acetylenecarboxylates under thermal conditions in the presence of LiClO4 or, alternatively, under high-pressure conditions (5 kbar) at room temperature yielding thiopyran derivatives. The hetero-Diels–Alder reaction occurs in a chemo- and regioselective manner. The initially formed [4 + 2] cycloadducts rearrange via a 1,3-hydrogen shift sequence to give the final products. The latter were smoothly oxidized by treatment with mCPBA to the corresponding sulfones.

Keywords

• dimethyl acetylenedicarboxylate (DMAD)
• hetero-Diels–Alder reactions
• high pressure reactions
• methyl propiolate
• thioketones
• thiopyrans