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Abstract:

Figure presented. 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 (Me 3Si)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. © 2010 American Chemical Society.

Registro:

Documento: Artículo
Título:(Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water
Autor:Barata-Vallejo, S.; Postigo, A.
Filiación:Faculty of Science, University of Belgrano, Villanueva 1324 CP, 1426-Buenos Aires, Argentina
Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, 3er piso, CP 1428-Buenos Aires, Argentina
Palabras clave:Azo compound; Carbon-carbon bond formation reactions; Dioxygens; Double bonds; Electron withdrawing group; Electron-rich alkenes; Fluorinated materials; Fluorophors; Fluorous; Good yield; H-atom abstraction; Intermolecular additions; Organic substrate; Perfluoroalkyl radicals; Perfluoroalkylation; Radical carbon; Radical initiators; Radical reactions; Silyl radical; Solvent effects; Substituted compounds; Synthetic chemists; Thermal decompositions; Unsaturated bonds; Chemical bonds; Olefins; Organic solvents; Paraffins; Pyrolysis; Reaction intermediates; Reaction kinetics; Addition reactions; 1,1' azobis(cyclohexanecarbonitrile); alkane derivative; alkene derivative; alkyl group; borane derivative; carbon; cyanide; oxygen; perfluoroalkyl; silane; silylhydroborane; unclassified drug; water; alkene; fluorinated hydrocarbon; free radical; silicone derivative; water; alkylation; article; chemical bond; perfluoroalkylation; structure analysis; substitution reaction; synthesis; chemical structure; chemistry; stereoisomerism; Alkenes; Alkylation; Free Radicals; Hydrocarbons, Fluorinated; Molecular Structure; Silicones; Stereoisomerism; Water
Año:2010
Volumen:75
Número:18
Página de inicio:6141
Página de fin:6148
DOI: http://dx.doi.org/10.1021/jo100901z
Título revista:Journal of Organic Chemistry
Título revista abreviado:J. Org. Chem.
ISSN:00223263
CODEN:JOCEA
CAS:carbon, 7440-44-0; cyanide, 57-12-5; oxygen, 7782-44-7; silane, 7803-62-5; water, 7732-18-5; Alkenes; Free Radicals; Hydrocarbons, Fluorinated; Silicones; Water, 7732-18-5
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v75_n18_p6141_BarataVallejo

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Citas:

---------- APA ----------
Barata-Vallejo, S. & Postigo, A. (2010) . (Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water. Journal of Organic Chemistry, 75(18), 6141-6148.
http://dx.doi.org/10.1021/jo100901z
---------- CHICAGO ----------
Barata-Vallejo, S., Postigo, A. "(Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water" . Journal of Organic Chemistry 75, no. 18 (2010) : 6141-6148.
http://dx.doi.org/10.1021/jo100901z
---------- MLA ----------
Barata-Vallejo, S., Postigo, A. "(Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water" . Journal of Organic Chemistry, vol. 75, no. 18, 2010, pp. 6141-6148.
http://dx.doi.org/10.1021/jo100901z
---------- VANCOUVER ----------
Barata-Vallejo, S., Postigo, A. (Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water. J. Org. Chem. 2010;75(18):6141-6148.
http://dx.doi.org/10.1021/jo100901z