Catalytic Oxidation of Partially and Fully Fluorinated Olefins with Osmium Tetroxide

A commonly held conception must be revised. The OsO 4 ‐catalyzed cis ‐hydroxylation of olefins was never tested with fluorinated olefins, because it was assumed that electron‐poor olefins would not react with OsO 4 . But under the standard reaction conditions even perfluorinated olefins can be converted into osmate esters such as 1 quickly and quantitatively. Their subsequent hydrolysis provides cis ‐diols, ketones, or 1,2‐diketones.