Heterogeneously catalyzed decarbonylation of thioesters by supported Ni, Pd, or Rh nanoparticle catalysts.

Abstract

Decarbonylation of thioesters has been actively studied using homogeneous metal catalysts as an attractive approach for synthesizing thioethers, which are widely utilized in various fields, because decarbonylation ideally requires no additives and produces CO as the sole theoretical byproduct. However, heterogeneously catalyzed decarbonylation of thioesters has not been reported to date, despite its importance for the construction of environmentally-friendly and practical catalytic systems. This study demonstrated a heterogeneously catalyzed system for the decarbonylation of various aryl thioesters to produce thioethers and CO by utilizing CeO2- or hydroxyapatite-supported Ni, Pd, or Rh nanoparticle catalysts. The Ni catalysts showed high catalytic activity, while the Pd catalysts possessed excellent functional group tolerance. The Rh catalysts were suitable for the selective decarbonylation of unsymmetrically substituted thioesters.