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In contrast to the previously reported intramolecular aryl migration, we present the selective sulfenylation of ortho-trifluoromethanesulfonate (OTf) substituted diaryliodonium salts with thiols. As such, diarylsulfides bearing vicinal OTf groups were synthesized in good yields. The unique reactivity of the vicinal OTf group and the sulfur atom in arylsulfides offers further transformations.

Graphical abstract: Selective S-arylation of thiols with o-OTf-substituted diaryliodonium salts toward diarylsulfides

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