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An electrochemical protocol for the synthesis of sulfursulfoxonium ylides and 1,3-dithioketals by reacting sulfoxonium ylides with disulfides has been developed under simple and mild conditions. By changing the solubility of the raw materials and the dielectric parameters of the electrolyte, sulfurization enabled a selective dehydrogenation of C–S and the construction of 1,3-dithioketals. The transformation is an ideal approach to prepare organosulfur reagents with a broad functional group tolerance as well as high selectivity, which leads to vicinal difunctionalized organosulfur compounds.

Graphical abstract: Tunable electrochemical diverse sulfurization of sulfoxonium ylides with disulfides

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