beta-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. beta-Hydroxy sulfoxides were transformed by pyrolysis in the corresponding allylic alcohols. (C) 2000 Elsevier Science Ltd. Ail rights reserved.