Herein we develop a metal-free umpolung dehydroxytrifluoromethylthiolation of alcohols with commercially available PPh 3 and N -trifluoromethylthiophthalimide within 30 minutes. This protocol shows excellent functional group tolerance and high regioselectivity. The dehydroxytrifluoromethylthiolation of a series of natural products and drugs further demonstrates its practicality. Preliminary mechanistic studies suggest that PPh 3 is responsible for deoxygenation and the key trifluoromethylthiophosphonium ion may be hydrolyzed by H 2 O in solvent.
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