Deoxygenative perfluoroalkylthiolation reactions of readily available carboxylic acid derivatives have been developed using a series of 2-(perfluoroalkylthio)benzothiazolium (BT-SRF) reagents as convenient sources of perfluoroalkylthiolate anions. This method avoids pre-activation of the substrates and delivers rarely reported perfluoroalkyl thioesters featuring SRF groups up to C6F13. A survey of carboxylic acid substrates with the pentafluoroethylthiolating reagent BT-SC2F5 also revealed the generality of the approach as a method for accessing underexplored fluorinated compounds
