Alkyl–aryl exchange of thioethers via Pd-catalyzed inert C(sp3)–S bond cleavage

Catalytic molecular transformations via C(sp3)–S bond cleavage have been rarely explored compared with those via C(sp2)–S bond cleavage despite their synthetic utilities. Here, we have developed alkyl–aryl exchange of thioethers via catalytic non-radical cleavage of inert C(sp3)–S bonds by utilizing a supported Au–Pd alloy nanoparticle catalyst. Based on various control experiments, the C(sp3)–S bond cleavage was revealed to undergo starting from β-hydride elimination, thereby enabling the use of a wide range of alkyl groups differently from previous reports involving C(sp3)–S bond oxidative addition.