Stereochemical studies on the formation of α,β-epoxysulfones using α-chloro-β-hydroxysulfones of known configuration

Abstract

Substitution reactions adjacent to sulfonyl groups are known to proceed with difficulty, and there is evidence to suggest that these may not necessarily proceed by an SN2 pathway. The mechanism of these reactions could be studied in principle by using the conversion of α-chloro-β-hydroxysulfones of known configuration into α,β-epoxysulfones of known configuration. This paper describes results in which this has been attempted. However, the stereochemical aspects of the epoxide formation could not be assigned unequivocally because of the intervention of a very facile "retro-aldol" process when the chlorohydrins are subjected to treatment with bases, although the experimental results do suggest that the reaction does proceed in a regular SN2-like manner, with inversion at carbon. The X-ray crystal structures of two highly substituted α,β-epoxysulfones are presented, thus putting the structures, including stereochemistry, of a range of these compounds on firm ground.