Umpolung trifluoromethylthiolation of alcohols

Abstract

Herein we develop a metal-free umpolung dehydroxytrifluoromethylthiolation of alcohols with commercially available PPh₃ 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 PPh₃ is responsible for deoxygenation and the key trifluoromethylthiophosphonium ion may be hydrolyzed by H₂O in solvent.