Direct Dehydroxytrifluoromethylthiolation of Alcohols Using Silver(I) Trifluoromethanethiolate and Tetra-n-butylammonium Iodide

An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF3 and nBu4NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by changing the ratio of AgSCF3/nBu4NI. This protocol is tolerant of different functional groups and might be applicable to late‐stage trifluoromethylthiolation of alcohols. Silver bullet: A new strategy has been developed for the direct trifluoromethylthiolation of alkyl alcohols using AgSCF3 and nBu4NI. This protocol does not require the activation of alcohols in advance. A variety of alkyl alcohols bearing different functional groups were transformed into the corresponding alkyl trifluoromethyl sulfides in moderate to good yields.