Visible-Light-Driven Thioesterification of Aryl Halides with Potassium Thiocarboxylates: Transition-Metal Catalyst-Free Incorporation of Sulfur Functionalities into an Aromatic Ring

Reactions of acceptor-substituted aryl iodides and bromides with potassium thiocarboxylates under white light irradiation allow for the preparation of S-aryl thioesters including synthetically versatile S-aryl thioacetates. This transition-metal and external photocatalyst-free method features extremely mild reaction conditions compared with those used in transition-metal-catalyzed protocols. Reactions proceed via the initial formation of an electron donor-acceptor (EDA) complex in the ground state, which was supported by UV-vis spectra. Electron paramagnetic resonance (EPR) spin-trapping experiments using phenyl-N-tert-butylnitrone (PBN) have revealed the radical nature of the reaction.