Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates

A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron‐deficient phosphanes (C2F5)nPF3−n (n=0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)nF5−nP(CH2NMe2−CH2NMe2)] are converted into the corresponding phosphonium salts [(Me3PCH2NMe2]+[(C2F5)nF5−nP(CH2NMe2)]− by treatment with PMe3. In addition [(C2F5)3F2P(CH2NMe2CH2NMe2)] can undergo a 1,3‐methyl shift from the internal to the terminal nitrogen—a structural characterization was achieved from the CF3 analogue. Reaction of [(C2F5)3F2P(CH2NMeCH2NMe3)] and PMe3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C2F5)3F2P(CH2NMeCH2PMe3)], which was fully characterized by X‐ray diffraction analysis. Moreover, an efficient one‐pot synthesis of Cs+[(C2F5)3F2P(CH2NMe2)]− was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions. It′s down to the fluorine: Several novel functionalized perfluoroalkylfluorophosphates were synthesized via an efficient one‐pot synthesis, employing Me2NCH2F as an oxidizer. Subsequent treatment with electrophiles (RX), such as HCl or allyl bromides, leads to the formation of zwitterionic ammonium phosphates (see scheme).