Iron-mediated C(sp3) transthioetherification

Thioethers and disulfides are two sulfur-based functional groups commonly found in essential macronutrients, enzymes, therapeutics, materials, and agrochemicals. The ability to readily exchange one sulfur-containing unit for another through a single transthioetherification process presents an opportunity for facile sulfur group exchange. Despite the importance of thioethers, methods for transthioetherification remain limited to sp²-hybridized thioethers. Herein, we report the C(sp³) transthioetherification of benzylic thioethers with disulfide reagents mediated by iron. In addition to an iron source, use of substoichiometric benzylic bromide enables the reaction to be performed at lower temperatures. The reaction is operable with substrates containing diverse functionality on both the carbon and disulfide coupling partners, and the final product concentration can be influenced with higher loadings of disulfide starting material.