Activation of weak nucleophiles: polyfluorocarbamates from polyfluoroalcohols via a fast radical reaction

作者：Soto Marc; Comalrena Helena; Balduzzi Ursula; Guirado Gonzalo; Lloveras Vega; Vidal Gancedo Jose; Maria Sebastian Rosa; Marquet Jordi

来源：Tetrahedron Letters, 2013, 54(47): 6310-6313.

DOI：10.1016/j.tetlet.2013.09.037

• Polyfluorocarbamates
• Single electron transfer
• Radical chain reaction
• Electron paramagnetic resonance
• Cyclic voltammetry

A new fast radical mechanism has been observed for the reaction of polyfluorinated alcohols and phenylisocyanate, very sensitive to the change of solvents and the concentration of reactants. The acidity of polyfluoroalcohols seems to be responsible for the observed new reactivity and evidences from kinetic studies, electron paramagnetic resonance, cyclic voltammetry, and photostimulation suggest that polyfluoroalkoxy radical is the key intermediate in the chain. To the best of our knowledge, it is the first time that a radical mechanism is described for the preparation of carbamates.

• 出版日期2013-11-20