Stereospecific Dehydroxytrifluoromethylthiolation of Alcohols Promoted by a Combination of Hypervalent Trifluoromethylthio-iodine(III) Reagent and N-Heterocyclic Carbene.

Direct dehydroxytrifluoromethylthiolation of alcohols is an attractive strategy for accessing CF 3 S-containing compounds. Herein, we report a method for dehydroxytrifluoromethylthiolation of alcohols by using the combination of hypervalent iodine(III) reagent TFTI and N-heterocyclic carbenes. This method shows excellent stereospecificity and chemoselectivity to give a product with clean inversion of the configuration of hydroxyl groups as well as can be used for late-stage modification of structurally complex alcohols. The reaction mechanism is proposed with experimental and computational evidence.