Copper-Catalyzed Direct Thiolation of Pentafluorobenzene with Diaryl Disulfides or Aryl Thiols by C-H and C-F Bond Activation

A Cu‐catalyzed cross‐coupling reaction of diaryl disulfides or aryl thiols with pentafluorobenzene using CuBr as the catalyst, tBuOLi or tBuOK as the base in DMSO at 60 °C under an O2 atmosphere was investigated. The corresponding bisarylthiolation products were obtained in moderate to good yields by C–H bond and C–F bond activation. When 1,10‐phenanthroline·H2O and DDQ were added to the above system, monoarylthiolation products, with/without bisarylthiolation products, could be isolated in moderate yields. A plausible mechanism for these transformations was given. Thus, it represents a method for the synthesis of polyfluorinated diaryl sulfides and polyfluorinated triarylbisulfides throughC–H bond and C–F bond activation. The Cu‐catalyzed cross‐coupling of diaryl disulfides/thiols with pentafluorobenzene in the presence of CuBr and tBuOLi or tBuOK in DMSO at 60 °C under an O2 atmosphere was investigated. The corresponding bisarylthiolation products wereobtained by C–H bond and C–F bond activation. When 1,10‐phenanthroline·H2O and DDQ were added to the above system, monoarylthiolation products could be isolated.