Heptafluoroisopropylthiolation of benzyl halides

• Heptafluoroisopropylthiolation of benzyl halides by a hexafluoropropylene (HFP)/CsF/S 8 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(CF 3 ) 2 ) has bioactivities in insecticidal molecules, but the protocol for direct introduction of -SCF(CF 3 ) 2 is under-explored. Described here is a protocol on heptafluoroisopropylthiolation of benzyl halides with a hexafluoropropylene (HFP)/CsF/S 8 system. The reaction enables the rapid construction of a range of (CF 3 ) 2 CFS-containing compounds from readily available materials. This protocol may find application in the synthesis of (CF 3 ) 2 CFS-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.