Buchwald-Hartwig Amination and C-S/S-H Metathesis of Aryl Sulfides by Selective C-S Cleavage Mediated by Air- and Moisture- Stable [Pd(NHC)(μ-Cl)Cl]2 Precatalysts: Unified Mechanism for Activation of Inert C-S Bonds

We report a combined experimental and mechanistic study on the Buchwald-Hartwig amination and C-S/S-H metathesis of aryl sulfides by selective activation of C-S bonds mediated by well-defined, air-and moisture-stable Pd(II)-NHC precatalysts, [Pd(NHC)(mu-Cl)Cl]2. This class of Pd(II)-NHC precatalysts displays excellent activity in the cross coupling of aryl sulfides. Most crucially, we unravel the unified mechanism for activation of C-S bonds in the C-N cross-coupling and C-S metathesis manifolds, where the inert C-S bond serves as a precursor to valuable amine or thioether products.

Automated summary

In this study, the excellent activity of [Pd(NHC)(μ-Cl)Cl]2 pre-catalysts in both the Buchwald-Hartwig amination and C-S/S-H metathesis reactions was demonstrated. The unified mechanism for the activation of C-S bonds in these reactions, where the inert C-S bond serves as a precursor to valuable products, was also elucidated.