Fluoro alcohol as reaction medium: one-pot synthesis of β-hydroxy sulfoxides from epoxides

β-Hydroxy sulfoxides were obtained in one-pot synthesis by the ring opening of oxiranes with thiols in hexafluoroisopropanol (HFIP) without any catalyst, followed by in situ oxidation under neutral conditions. The reaction is anti-selective. β-Hydroxy sulfoxides were transformed by pyrolysis in the corresponding allylic alcohols.