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

Marc Soto; Helena Comalrena; Ursula Balduzzi; Gonzalo Guirado; Vega Lloveras; José Vidal-Gancedo; Rosa María Sebastián; Jordi Marquet

doi:10.1016/j.tetlet.2013.09.037

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

Marc Soto, Helena Comalrena, Ursula Balduzzi, Gonzalo Guirado, Vega Lloveras, José Vidal-Gancedo, Rosa María Sebastián, Jordi Marquet

Research output: Contribution to journal › Article › Research › peer-review

1 Citation (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	6310-6313
Journal	Tetrahedron Letters
Volume	54
Issue number	47
DOIs	https://doi.org/10.1016/j.tetlet.2013.09.037
Publication status	Published - 20 Nov 2013

Keywords

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

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10.1016/j.tetlet.2013.09.037

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title = "Activation of weak nucleophiles: Polyfluorocarbamates from polyfluoroalcohols via a fast radical reaction",

abstract = "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. {\textcopyright} 2013 Elsevier Ltd. All rights reserved.",

keywords = "Cyclic voltammetry, Electron paramagnetic resonance, Polyfluorocarbamates, Radical chain reaction, Single electron transfer",

author = "Marc Soto and Helena Comalrena and Ursula Balduzzi and Gonzalo Guirado and Vega Lloveras and Jos{\'e} Vidal-Gancedo and Sebasti{\'a}n, {Rosa Mar{\'i}a} and Jordi Marquet",

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doi = "10.1016/j.tetlet.2013.09.037",

language = "English",

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Activation of weak nucleophiles: Polyfluorocarbamates from polyfluoroalcohols via a fast radical reaction. / Soto, Marc; Comalrena, Helena; Balduzzi, Ursula; Guirado, Gonzalo; Lloveras, Vega; Vidal-Gancedo, José; Sebastián, Rosa María ; Marquet, Jordi.

In: Tetrahedron Letters, Vol. 54, No. 47, 20.11.2013, p. 6310-6313.

Research output: Contribution to journal › Article › Research › peer-review

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

IS - 47

ER -

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

Abstract

Keywords

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