This study investigates the (3 + 2) cycloaddition of substituted cyclopropenones with elemental sulfur. Combined experimental and computational results highlight the involvement of reactive sulfur species, such as those generated from KF or sulfide impurities. Oxygen exerts minimal influence, whereas oxidants such as BQ or m-CPBA completely suppress the reaction. DFT calculations challenge conventional S8-based mechanisms, pointing to an energetically costly process from inactivated S8. Our results support that the cyclic S8 molecules of elemental sulfur are inactive toward cyclopropenone reagents. The true reactive species are polysulfide anions, which can be present in different forms (FSn-, HSn-, or Sn2-) depending on the additive type and purity of the sulfur source. These species undergo conjugate addition to the least substituted carbon of the cyclopropenone C═C bond, ultimately affording a five-membered heterocycle─1,2-dithiol-3-one─as a single regioisomer, through a ketenethialdehyde and thiet-2-one sequence.
Rivero et al. (Wed,) studied this question.