Heptafluoroisopropylthiolation of benzyl halides

•Heptafluoroisopropylthiolation of benzyl halides by a hexafluoropropylene (HFP)/CsF/S8 system was achieved.•A wide substrate scope and good functional group tolerance were observed.•Readily available and economic starting materials were used in this protocol. Heptafluoroisopropylthio group (-SCF(CF3)2) has bioactivities in insecticidal molecules, but the protocol for direct introduction of -SCF(CF3)2 is under-explored. Described here is a protocol on heptafluoroisopropylthiolation of benzyl halides with a hexafluoropropylene (HFP)/CsF/S8 system. The reaction enables the rapid construction of a range of (CF3)2CFS-containing compounds from readily available materials. This protocol may find application in the synthesis of (CF3)2CFS-containing biologically active molecules. Heptafluoroisopropylthiolation of benzyl halides under mild conditions. Extended to various electron-rich benzyl halides. Electron-deficient benzyl halides can be obtained smoothly as well. [Display omitted]