Do the Electronic Effects of Sulfur Indeed Control the π-Selectivity of γ-Sulfenyl Enones? An Investigation^†

The electronic effects of sulfur in γ-sulfenyl enones are not transmitted to the carbonyl carbon through the π bond as reported previously. The diastereoselectivity is rather controlled by a combination of several other factors. The steric effects arising from the substituents on the sulfur atom and the γ-carbon and the bulk of the nucleophile constitute the major control elements.