✍ Scribed by Denise Curi; Vera L. Pardini; Hans Viertler; Alfons L. Baumstark; Donald B. Harden Jr.
No coin nor oath required. For personal study only.
The oxidation of a series of ketene‐S,S‐acetals, 2a–f, and a series of thioacetals and thioketals, 4a–g, with a fourfold or greater excess of dimethyldioxirane, 1, produced the corresponding bis‐sulfones 3a–f and 5a–g in excellent yields. The reaction of the bis‐sulfides with one, two, and three equivalents of 1 yielded monosulfoxides, bis‐sulfoxides, and sulfoxide‐sulfones, respectively, as the major products. The order of addition of the reactants as well as the temperature of the reaction mixture changed the product distributions. The use of low‐temperature, rapid stirring and the addition of the dioxirane solution to the bis‐sulfide maximized the yield of the major product. The results are consistent with an electrophilic oxygen‐atom transfer mechanism in which the rate of sulfide oxidation is much faster than oxidation of sulfoxide to sulfone. However, sulfoxide oxidation is of a sufficient rate such that local concentration effects affect the results.
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