TY - JOUR
T1 - Activation of weak nucleophiles: Polyfluorocarbamates from polyfluoroalcohols via a fast radical reaction
AU - Soto, Marc
AU - Comalrena, Helena
AU - Balduzzi, Ursula
AU - Guirado, Gonzalo
AU - Lloveras, Vega
AU - Vidal-Gancedo, José
AU - Sebastián, Rosa María
AU - Marquet, Jordi
PY - 2013/11/20
Y1 - 2013/11/20
N2 - 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. © 2013 Elsevier Ltd. All rights reserved.
AB - 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. © 2013 Elsevier Ltd. All rights reserved.
KW - Cyclic voltammetry
KW - Electron paramagnetic resonance
KW - Polyfluorocarbamates
KW - Radical chain reaction
KW - Single electron transfer
U2 - 10.1016/j.tetlet.2013.09.037
DO - 10.1016/j.tetlet.2013.09.037
M3 - Article
VL - 54
SP - 6310
EP - 6313
JO - Tetrahedron Letters
JF - Tetrahedron Letters
SN - 0040-4039
IS - 47
ER -