Synthesis of Thioesters from Aldehydes via N‐Heterocyclic Carbene (NHC) Catalyzed Radical Relay

Abstract We have developed an efficient N‐heterocyclic carbene (NHC)‐catalyzed thioesterification of aldehydes using N‐thiosuccinimides as the thiolation reagent. This organocatalyzed transition involves the generation of sulfur radicals by single electron transfer of the Breslow enolate (generated from aldehyde and NHC catalyst) with N‐thiosuccinimides. This method offers facile access to various highly functionalized thioesters and exhibits good chemical yields and functional group tolerance.