Silver‐ or Photopromoted Ring‐Opening Trifluoromethylselenolation of Epoxides With [Me ₄ N][SeCF ₃ ]

Silver‐ or photopromoted trifluoromethylselenolative difunctionalization of epoxides with [Me ₄ N][SeCF ₃ ] is described. A series of epoxides reacted with [Me ₄ N][SeCF ₃ ] and carboxylic acids in acetone in the presence of AgClO ₄ at 60 °C for 16 h to furnish the corresponding trifluoromethylselenyl esters in up to 92% yield. While the reactions of epoxides with [Me ₄ N][SeCF ₃ ] were performed in aqueous acetone at room temperature under purple light‐emitting diodes irradiation for 16 h, the respective hydroxytrifluoromethylselenolated products were obtained in up to 86% yield. These methods exhibit mild reaction conditions, high efficiency, and good functional group tolerance, enabling concise and atom‐economical synthesis of CF ₃ Se‐containing multi‐functionalized molecules from epoxides.