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By utilizing elemental sulfur as the thiolation agent and oxidant, a copper-catalyzed direct C–H bond thiolation of electron-deficient arenes was demonstrated. Various electron-deficient arenes were proved to be suitable for this transformation. Preliminary mechanistic studies indicated that this reaction underwent a radical pathway, in which the trisulfur radical anion (S3˙) might play a vital role. Meanwhile, KIE experiments suggested that C–H bond cleavage was not involved in the rate-determining step.

Graphical abstract: Elemental sulfur as a sulfuration agent in the copper-catalyzed C–H bond thiolation of electron-deficient arenes

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