Visible-Light-Driven Thioesterification of Aryl Halides with Potassium Thiocarboxylates: Transition-Metal Catalyst-Free Incorporation of Sulfur Functionalities into an Aromatic Ring
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Updated: Sep 21, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Alexey A Volkov1, Dmitry I Bugaenko1, Alexey V Bogdanov1
1Department of Chemistry, Moscow State University, Moscow 119234, Russia.
Abstract:
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.
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