Heterogeneously catalyzed thioether metathesis by a supported Au-Pd alloy nanoparticle design based on Pd ensemble control.

C-S bond metathesis of thioethers has gained attention as a new approach to the late-stage diversification of already existing useful thioethers with molecular frameworks intact. However, direct or indirect thioether metathesis is scarcely reported, and heterogeneously catalyzed systems have not been explored. Here, we develop heterogeneously catalyzed direct thioether metathesis using a supported Au-Pd alloy nanoparticle catalyst with a high Au/Pd ratio. The Au-diluted Pd ensembles suppress the strong π-adsorption of diaryl thioethers on the nanoparticles and promote transmetalation via thiolate spill-over onto neighboring Au species, enabling an efficient direct thioether metathesis.