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

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.