Structure–activity relationships in Pd catalysed C–S activation of thioesters

Abstract

Transition metal catalyzed C–S activation has recently become a powerful strategy in organic synthesis, and has shown great potential in petroleum chemistry and protein synthesis. Nonetheless, the inherent structure–activity relationships have been less-well understood, limiting the future development and applications of such protocols. In this study, we carried out a systematic investigation on Pd(0) catalysed C–S activation using density functional theory (DFT) methods. The C–S bond activation of 34 structurally independent thioesters (R¹COSR²) was studied. The correlations between the activation barrier, C–S bond dissociation enthalpy (BDE), the reaction energy and structural parameters of the involving intermediates and transition states were systematically examined.