Direct thioether metathesis enabled by in situ formed Pd nanocluster catalysts

Abstract

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.