CaCl2-Promoted Dehydroxytrifluoromethylselenolation of Alcohols with [Me4N][SeCF3].

A direct trifluoromethylselenolation of alcohols with the readily accessible [Me4N][SeCF3] salt has been reported. The reaction is significantly promoted by CaCl2 and proceeds smoothly through unprecedented carbonoselenoate intermediates to form the corresponding alkyl trifluoromethyl selenoethers in good yields. This protocol is also applicable to the late-stage dehydroxytrifluoromethylselenolation of complex alcohols owing to its mildness, good compatibility, high efficiency, and broad functional group tolerance.