Visible Light and Hydroxynaphthylbenzimidazoline Promoted Transition-Metal-Catalyst-Free Desulfonylation of N-Sulfonylamides and N-Sulfonylamines

The Journal of Organic Chemistry
Eietsu HasegawaKan Wakamatsu

Abstract

A visible light promoted process for desulfonylation of N-sulfonylamides and -amines has been developed, in which 1,3-dimethyl-2-hydroxynaphthylbenzimidazoline (HONap-BIH) serves as a light absorbing, electron and hydrogen atom donor, and a household white light-emitting diode serves as a light source. The process transforms various N-sulfonylamide and -amine substrates to desulfonylated products in moderate to excellent yields. The observation that the fluorescence of 1-methyl-2-naphthoxy anion is efficiently quenched by the substrates suggests that the mechanism for the photoinduced desulfonylation reaction begins with photoexcitation of the naphthoxide chromophore in HONap-BIH, which generates an excited species via intramolecular proton transfer between the HONap and BIH moieties. This process triggers single electron transfer to the substrate, which promotes loss of the sulfonyl group to form the free amide or amine. The results of studies employing radical probe substrates as well as DFT calculations suggest that selective nitrogen-sulfur bond cleavage of the substrate radical anion generates either a pair of an amide or amine anion and a sulfonyl radical or that of an amidyl or aminyl radical and sulfinate anion, dependi...Continue Reading

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Citations

Jul 4, 2019·Chemical Society Reviews·Alexey A FestaErik V Van der Eycken
Oct 15, 2019·Angewandte Chemie·Simon RohrbachJohn A Murphy
Oct 2, 2020·Angewandte Chemie·Matthias SchmalzbauerBurkhard König
Aug 14, 2021·Chemical Reviews·Xue-Qiang ChuChao-Jun Li
Jun 3, 2020·The Journal of Organic Chemistry·Cameron J HunterRobert Fimognari
Aug 20, 2021·Chemistry : a European Journal·Tomoya OzakiGregory J P Perry

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