(Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water

Perfluoroalkyl-substituted compounds are regarded as important components of fluorophors and for the introduction of fluorous tags into organic substrates. Their syntheses in organic solvents are achieved through different methods, among which, the addition of perfluoroalkyl radicals to unsaturated...

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Detalles Bibliográficos
Autores principales: Barata-Vallejo, Sebastián, Postigo, Al
Formato: Artículo
Lenguaje:Inglés
Publicado: Universidad de Belgrano - Facultad de Ciencias Exactas y Naturales - Proyectos de Investigación 2014
Materias:
Reactions of Olefins in Water
Mediated Intermolecular
mediada intermolecular
Reacciones de olefinas en Agua
Acceso en línea:http://repositorio.ub.edu.ar/handle/123456789/2720
Aporte de:
Repositorio Institucional - Universidad de Belgrano (UB) de Universidad de Belgrano
id I36-R142-123456789-2720
record_format dspace
institution Universidad de Belgrano
institution_str I-36
repository_str R-142
collection Repositorio Institucional - Universidad de Belgrano (UB)
language Inglés
topic Reactions of Olefins in Water
Mediated Intermolecular
mediada intermolecular
Reacciones de olefinas en Agua
spellingShingle Reactions of Olefins in Water
Mediated Intermolecular
mediada intermolecular
Reacciones de olefinas en Agua
Barata-Vallejo, Sebastián
Postigo, Al
(Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water
topic_facet Reactions of Olefins in Water
Mediated Intermolecular
mediada intermolecular
Reacciones de olefinas en Agua
description Perfluoroalkyl-substituted compounds are regarded as important components of fluorophors and for the introduction of fluorous tags into organic substrates. Their syntheses in organic solvents are achieved through different methods, among which, the addition of perfluoroalkyl radicals to unsaturated bonds represents a convenient choice. On the other hand, intermolecular radical reactions in water have attracted the attention of synthetic chemists as a strategic route to carbon−carbon bond formation reactions. In this paper we undertook the intermolecular addition of perfluoroalkyl radicals on electron rich alkenes and alkenes with electron withdrawing groups in water, mediated by silyl radicals, and obtained perfluoroalkyl-substituted compounds in fairly good yields. The radical triggering events employed consist of the thermal decomposition of an azo compound and the dioxygen initiation. Our results indicate that for intermolecular carbon−carbon bond formation reactions mediated by (Me3Si)3SiH, the decomposition of the azo compound 1,1′-azobis(cyclohexanecarbonitrile) (ACCN) is the best radical initiator. We also found that water exerts a relevant solvent effect on the rates of perfluoroalkyl radical additions onto double bonds and the H atom abstraction from the silane. Our account provides a versatile and convenient method to achieve perfluoroalkylation reactions of alkenes in water to render perfluoroalkylated alkanes as key intermediates in the synthesis of fluorophors and other fluorinated materials. This is the first report where perfluoroalkyl-substituted alkanes are synthesized through intermolecular radical carbon−carbon bond formation reactions in water, mediated by silyl radicals.
format Article
author Barata-Vallejo, Sebastián
Postigo, Al
author_facet Barata-Vallejo, Sebastián
Postigo, Al
author_sort Barata-Vallejo, Sebastián
title (Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water
title_short (Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water
title_full (Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water
title_fullStr (Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water
title_full_unstemmed (Me3Si)3SiH-Mediated Intermolecular Radical Perfluoroalkylation Reactions of Olefins in Water
title_sort (me3si)3sih-mediated intermolecular radical perfluoroalkylation reactions of olefins in water
publisher Universidad de Belgrano - Facultad de Ciencias Exactas y Naturales - Proyectos de Investigación
publishDate 2014
url http://repositorio.ub.edu.ar/handle/123456789/2720
work_keys_str_mv AT baratavallejosebastian me3si3sihmediatedintermolecularradicalperfluoroalkylationreactionsofolefinsinwater
AT postigoal me3si3sihmediatedintermolecularradicalperfluoroalkylationreactionsofolefinsinwater
bdutipo_str Repositorios
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