Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis

Autores
Garcia Liñares, Guadalupe Eugenia; Arroyo Mañez, Pau; Baldessari, Alicia
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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.
Fil: Garcia Liñares, Guadalupe Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Fil: Arroyo Mañez, Pau. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Fil: Baldessari, Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Materia
Enzyme Catalysis
Molecular Modeling
Reaction Mechanism
Amides
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/18715
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/18715
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network_name_str CONICET Digital (CONICET)
spelling Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic AminolysisGarcia Liñares, Guadalupe EugeniaArroyo Mañez, PauBaldessari, AliciaEnzyme CatalysisMolecular ModelingReaction MechanismAmideshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A 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.Fil: Garcia Liñares, Guadalupe Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Arroyo Mañez, Pau. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Baldessari, Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaWiley VCH Verlag2014-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/18715Garcia Liñares, Guadalupe Eugenia; Arroyo Mañez, Pau; Baldessari, Alicia; Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis; Wiley VCH Verlag; European Journal of Organic Chemistry; 2014; 29; 10-2014; 6439-64501434-193XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201402749info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201402749/abstractinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:18:53Zoai:ri.conicet.gov.ar:11336/18715instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:18:53.671CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
title Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
spellingShingle Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
Garcia Liñares, Guadalupe Eugenia
Enzyme Catalysis
Molecular Modeling
Reaction Mechanism
Amides
title_short Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
title_full Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
title_fullStr Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
title_full_unstemmed Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
title_sort Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis
dc.creator.none.fl_str_mv Garcia Liñares, Guadalupe Eugenia
Arroyo Mañez, Pau
Baldessari, Alicia
author Garcia Liñares, Guadalupe Eugenia
author_facet Garcia Liñares, Guadalupe Eugenia
Arroyo Mañez, Pau
Baldessari, Alicia
author_role author
author2 Arroyo Mañez, Pau
Baldessari, Alicia
author2_role author
author
dc.subject.none.fl_str_mv Enzyme Catalysis
Molecular Modeling
Reaction Mechanism
Amides
topic Enzyme Catalysis
Molecular Modeling
Reaction Mechanism
Amides
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 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.
Fil: Garcia Liñares, Guadalupe Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Fil: Arroyo Mañez, Pau. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Fil: Baldessari, Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
description 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.
publishDate 2014
dc.date.none.fl_str_mv 2014-10
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/18715
Garcia Liñares, Guadalupe Eugenia; Arroyo Mañez, Pau; Baldessari, Alicia; Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis; Wiley VCH Verlag; European Journal of Organic Chemistry; 2014; 29; 10-2014; 6439-6450
1434-193X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/18715
identifier_str_mv Garcia Liñares, Guadalupe Eugenia; Arroyo Mañez, Pau; Baldessari, Alicia; Lipase-Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis; Wiley VCH Verlag; European Journal of Organic Chemistry; 2014; 29; 10-2014; 6439-6450
1434-193X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201402749
info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201402749/abstract
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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