Exploration of 2-(pentafluoro-λ6-sulfanyl)ethane-1-sulfonyl chloride as a novel pentafluorosulfanylation reagent

• A novel pentafluorosulfanylation reagent is reported. • 2-(Pentafluoro-λ 6 -sulfanyl)ethane-1-sulfonyl chloride is prepared from vinyl acetate in 5 steps. • Its reaction with substituted-phenylvinyl acetates under photoredox catalysis provided the corresponding α-SF 5 -ketones. In this paper, we report our initial results on the development of 2-(pentafluoro-λ 6 -sulfanyl)ethane-1-sulfonyl chloride as a novel pentafluorosulfanylation reagent. The targeted reagent was synthesized in five steps from vinyl acetate. As opposed to gaseous SF 5 Cl, 2-(pentafluoro-λ 6 -sulfanyl)ethane-1-sulfonyl chloride is a liquid under ambient conditions. Its reaction with substituted-phenylvinyl acetates under photoredox catalysis provided the corresponding α-SF 5 -ketones in low to moderate yields due in part to an incomplete desulfonylation step. Nonetheless, these results serve as a promising starting point for the further development of pentafluorosulfanylation reagent.