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dc.contributor.author
Barata Vallejo, Sebastian  
dc.contributor.author
Postigo, Jose Alberto  
dc.date.available
2020-03-02T19:37:47Z  
dc.date.issued
2010-09  
dc.identifier.citation
Barata Vallejo, Sebastian; Postigo, Jose Alberto; (Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water; American Chemical Society; Journal of Organic Chemistry; 75; 18; 9-2010; 6141-6148  
dc.identifier.issn
0022-3263  
dc.identifier.uri
http://hdl.handle.net/11336/98658  
dc.description.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.  
dc.format
application/pdf  
dc.language.iso
eng  
dc.publisher
American Chemical Society  
dc.rights
info:eu-repo/semantics/openAccess  
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/  
dc.subject
radical chemistry  
dc.subject
radical reactions  
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silyl radicals  
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radical perfluoroalkylation in water  
dc.subject.classification
Química Orgánica  
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Ciencias Químicas  
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CIENCIAS NATURALES Y EXACTAS  
dc.title
(Me3Si)3SiH-mediated intermolecular radical perfluoroalkylation reactions of olefins in water  
dc.type
info:eu-repo/semantics/article  
dc.type
info:ar-repo/semantics/artículo  
dc.type
info:eu-repo/semantics/publishedVersion  
dc.date.updated
2020-02-27T18:50:39Z  
dc.journal.volume
75  
dc.journal.number
18  
dc.journal.pagination
6141-6148  
dc.journal.pais
Estados Unidos  
dc.journal.ciudad
Washington  
dc.description.fil
Fil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina  
dc.description.fil
Fil: Postigo, Jose Alberto. Universidad de Belgrano; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina  
dc.journal.title
Journal of Organic Chemistry  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jo100901z  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/jo100901z