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Abstract:

A series of hydroxy-, methoxy-, and nitrophenylacetamides was synthesized by enzyme catalysis. The 28 new products were obtained through a lipase-catalyzed two-step reaction in very good to excellent yield. In the case of nitro derivatives, a one-pot, two-step methodology allowed the desired products to be obtained in high yields. The influence of various reaction parameters in the lipase-catalyzed reactions, such as enzyme source, nucleophile (alcohol or amine)/substrate ratio, enzyme/substrate ratio, solvent and temperature were studied. It was observed that nitro-substituted phenylacetates were more reactive in the aminolysis reaction than phenylacetates substituted with a hydroxyl group. To study this substituent effect, a Hammett analysis and the determination of the ρ parameter were carried out. Moreover, a computational study was applied to the most representative systems, performing an exploration of the potential energy surface for the catalyzed and noncatalyzed aminolysis reaction for nitro- and hydroxyphenylacetates. Both analysis showed that the presence of a strongly electron-attracting group favors the activity of the enzyme, in complete agreement with the experimental results of the enzymatic catalysis. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA.

Registro:

Documento: Artículo
Título:Lipase-catalyzed synthesis of substituted phenylacetamides: Hammett analysis and computational study of the enzymatic aminolysis
Autor:García Liñares, G.; Arroyo Mañez, P.; Baldessari, A.
Filiación:Laboratorio de Biocatálisis, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, piso 3, Buenos Aires, C1428EGA, Argentina
Laboratorio de Modelado Molecular, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, piso 3, Buenos Aires, C1428EGA, Argentina
Palabras clave:Amides; Enzyme catalysis; Esters; Molecular modeling; Reaction mechanisms
Año:2014
Volumen:2014
Número:29
Página de inicio:6439
Página de fin:6450
DOI: http://dx.doi.org/10.1002/ejoc.201402749
Título revista:European Journal of Organic Chemistry
Título revista abreviado:Eur. J. Org. Chem.
ISSN:1434193X
CODEN:EJOCF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1434193X_v2014_n29_p6439_GarciaLinares

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Citas:

---------- APA ----------
García Liñares, G., Arroyo Mañez, P. & Baldessari, A. (2014) . Lipase-catalyzed synthesis of substituted phenylacetamides: Hammett analysis and computational study of the enzymatic aminolysis. European Journal of Organic Chemistry, 2014(29), 6439-6450.
http://dx.doi.org/10.1002/ejoc.201402749
---------- CHICAGO ----------
García Liñares, G., Arroyo Mañez, P., Baldessari, A. "Lipase-catalyzed synthesis of substituted phenylacetamides: Hammett analysis and computational study of the enzymatic aminolysis" . European Journal of Organic Chemistry 2014, no. 29 (2014) : 6439-6450.
http://dx.doi.org/10.1002/ejoc.201402749
---------- MLA ----------
García Liñares, G., Arroyo Mañez, P., Baldessari, A. "Lipase-catalyzed synthesis of substituted phenylacetamides: Hammett analysis and computational study of the enzymatic aminolysis" . European Journal of Organic Chemistry, vol. 2014, no. 29, 2014, pp. 6439-6450.
http://dx.doi.org/10.1002/ejoc.201402749
---------- VANCOUVER ----------
García Liñares, G., Arroyo Mañez, P., Baldessari, A. Lipase-catalyzed synthesis of substituted phenylacetamides: Hammett analysis and computational study of the enzymatic aminolysis. Eur. J. Org. Chem. 2014;2014(29):6439-6450.
http://dx.doi.org/10.1002/ejoc.201402749