Combination of Lewis Basic Selenium Catalysis and Redox Selenium Chemistry: Synthesis of Trifluoromethylthiolated Tertiary Alcohols with Alkenes.

A new and efficient method for diaryl selenide catalyzed vicinal CFS hydroxylation of 1,1-multisubstitued alkenes has been developed. Various trifluoromethylthiolated tertiary alcohols could be readily synthesized under mild conditions. This method is also effective for the intramolecular cyclization of alkenes tethered by carboxylic acid, hydroxy, sulfamide, or ester groups and is associated with the introduction of a CFS group. Mechanistic studies have revealed that the pathway involves a redox cycle between Se(II) and Se(IV) and Lewis basic selenium catalysis.