An Electrophilic Trifluoromethylthiolation of Silylenol Ethers and β ‐Naphthols with Diethylaminosulfur Trifluoride and (Trifluoromethyl)trimethylsilane

An efficient and general trifluoromethylthiolation of silylenol ethers and β ‐naphthols have been accomplished employing the combination of diethylaminosulfur trifluoride (DAST) and (trifluoromethyl)trimethylsilane (CF 3 TMS) as source of electrophilic trifluoromethylthio moiety for the synthesis of α ‐trifluoromethylthiolated carbonyl compounds and β ‐naphthols in good yields. Important features of this method include wide functional group tolerance and use of readily available DAST/CF 3 TMS. Potential of the methodology was demonstrated via the synthesis of α ‐trifluoromethylthiolated (+)‐4‐cholesten‐3‐one and naphthoquinone.