An operationally simple, practical, and efficient cascade
approach
employing α-allyl dithioesters and NBS/NIS has been achieved
to access a series of dihydrothiophenes and thiophenes containing
diverse functional groups of different electronic and steric natures
in good to excellent yields at room temperature in open air. The reaction
proceeds via the electrophilic addition of a halogen source (NBS/NIS)
to an allylic double bond, followed by intramolecular regio- and chemoselective S-cyclization. This protocol avoids potential toxicity and
tedious work-up conditions, and features easy synthesis from readily
available starting materials under catalyst-free conditions. Furthermore,
4,5-dihydrothiophenes were aromatized to thiophenes by treatment with
KOH in DMF at room temperature. A probable mechanism for the formation
of dihydrothiophenes and thiophenes from α-allyl dithioesters
has been suggested. Notably, a large-scale experiment and the transformations
of products indicated the potential utility of this reaction compared
to competing processes for the synthesis of 4,5-dihydrothiophenes
and thiophenes.