An efficient and straightforward approach for accessing thionoesters via palladium-catalyzed C–N cleavage of thioamides

Abstract

We first report the coupling of activated thioamides with alcohols to efficiently form thioesters via palladium-catalyzed C-N cleavage strategy. The new approach employs the thioamides as thioacylating reagent to give...

Esterification of Thioamides via Selective N–C(S) Cleavage under Mild Conditions

“…In this regard, two generic pathways have been developed: (1) transition-metal-catalyzed cross-coupling via acyl-metal intermediates and (2) transition-metal-free reactions via tetrahedral intermediates (Figure A) . Both reactivity frameworks are underpinned by the development of the concept of ground-state destabilization of the acyclic amide bond, where the amidic resonance (15–20 kcal/mol, n N → π* CO conjugation) is tailored by steric and electronic substitution in common amides .…”