Herein, we demonstrate the application of unsymmetrical iodonium salts towards S-arylation of glycosyl thiols under metal-free conditions, affording a various stereoretentive thioarylglycosides in moderate to good yields. The application of an inorganic base CsCO enables the C-S bond formation under mild and experimentally simple conditions at room temperature. The proper choice of auxiliary of the unsymmetrical iodonium salt enables the access to diverse functionalized aryl moieties including biphenyl groups and its incorporation into thioarylglycosides.
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