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

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• 作者：Marc Soto ; Helena Comalrena ; Ursula Balduzzi ; Gonzalo Guirado ; Vega Lloveras ; Jos¨¦ Vidal-Gancedo ; Rosa Mar¨ªa Sebasti¨¢n ; Jordi Marquet
• 关键词：LBYLIZZDCFLJKZ-UHFFFAOYSA-N
• 刊名：Tetrahedron Letters
• 出版年：2013
• 出版时间：20 November, 2013
• 年：2013
• 卷：54
• 期：47
• 页码：6310-6313
• 全文大小：565 K

文摘

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.