Direct thioether metathesis enabled by in situ formed Pd nanocluster catalysts

Thioether metathesis has been noted as a complementary thioether synthesis methodology with cross-coupling reactions, which can be applied to late-stage diversification. However, despite its utility, versatile direct C-S/C-S cross-metathesis of thioethers has not been previously reported. Herein, direct catalytic metathesis of various thioethers was enabled by Pd acetate and tricyclohexylphosphine precursors with no additives, affording unsymmetrical thioethers. Detailed characterization and control experiments confirmed that Pd(0) nanocluster homogeneous catalysts formed in situ are the actual active species enabling this versatile direct transformation. This work will pave the way for novel organic molecular transformations driven by metal nanocluster catalysts.

Automated summary

This research reports a new method for the synthesis of thioethers, utilizing Pd acetate and tricyclohexylphosphine precursors to catalyze the direct metathesis of thioethers without additives, resulting in high yields. Detailed studies indicate that Pd(0) nanocluster homogeneous catalysts are the actual active species, providing a new perspective for the metal nanocluster-catalyzed transformation of organic molecules.