Base‐Promoted Thioester Synthesis from Acyl Fluorides Using Sulfonyl Hydrazides as Thiol Surrogates

A method for synthesizing thioesters from acyl fluorides has been developed using sulfonyl hydrazides as thiol surrogates. The reaction proceeds under base‐promoted conditions, generating a diverse array of aryl thioesters in good‐to‐excellent yields with high functional‐group tolerance. Mechanistic studies reveal an initial ionic acyl substitution to form acyl sulfonyl hydrazide intermediates, followed by a radical process involving N 2 extrusion and the recombination of acyl and thio fragments to form the CS bond.