Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution

Autores
Peisino, Lucas Ernesto; Pierini, Adriana Beatriz
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The reaction of N-allyl-N-(2-halobenzyl)-acetamides and derivatives was investigated in liquid ammonia under irradiation with the nucleophiles Me3Sn−, Ph2P− and O2NCH2 −. Following this procedure, novel substituted 2- acetyl-1,2,3,4-tetrahydroisoquinolines and substituted 2-acetyl- 2,3,4,5-tetrahydro-1H-benzo[c]azepines were obtained in good yields. These reactions are proposed to occur through the intermediacy of aryl radicals, which by intramolecular 6-exo or 7-endo attack to a double bond cyclize to give aliphatic radicals, which react along the propagation steps of the SRN1 chain cycle to afford the cyclic substituted compounds as main products. The reactions were modeled with DFT methods, which provide a rational understanding that relates the product distribution to the structure of the aliphatic radicals proposed as intermediates and the kinetic of their formation.
Fil: Peisino, Lucas Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Pierini, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Intramolecular Cyclizations
Radicals
Computational Chemistry
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:11336/25405
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitutionPeisino, Lucas ErnestoPierini, Adriana BeatrizIntramolecular CyclizationsRadicalsComputational Chemistryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The reaction of N-allyl-N-(2-halobenzyl)-acetamides and derivatives was investigated in liquid ammonia under irradiation with the nucleophiles Me3Sn−, Ph2P− and O2NCH2 −. Following this procedure, novel substituted 2- acetyl-1,2,3,4-tetrahydroisoquinolines and substituted 2-acetyl- 2,3,4,5-tetrahydro-1H-benzo[c]azepines were obtained in good yields. These reactions are proposed to occur through the intermediacy of aryl radicals, which by intramolecular 6-exo or 7-endo attack to a double bond cyclize to give aliphatic radicals, which react along the propagation steps of the SRN1 chain cycle to afford the cyclic substituted compounds as main products. The reactions were modeled with DFT methods, which provide a rational understanding that relates the product distribution to the structure of the aliphatic radicals proposed as intermediates and the kinetic of their formation.Fil: Peisino, Lucas Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Pierini, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2013-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/25405Peisino, Lucas Ernesto; Pierini, Adriana Beatriz; Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution; American Chemical Society; Journal of Organic Chemistry; 78; 10; 4-2013; 4719-47290022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo4001788info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jo4001788info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:25:22Zoai:ri.conicet.gov.ar:11336/25405instacron: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:34982025-10-15 14:25:22.811CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
title Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
spellingShingle Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
Peisino, Lucas Ernesto
Intramolecular Cyclizations
Radicals
Computational Chemistry
title_short Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
title_full Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
title_fullStr Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
title_full_unstemmed Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
title_sort Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution
dc.creator.none.fl_str_mv Peisino, Lucas Ernesto
Pierini, Adriana Beatriz
author Peisino, Lucas Ernesto
author_facet Peisino, Lucas Ernesto
Pierini, Adriana Beatriz
author_role author
author2 Pierini, Adriana Beatriz
author2_role author
dc.subject.none.fl_str_mv Intramolecular Cyclizations
Radicals
Computational Chemistry
topic Intramolecular Cyclizations
Radicals
Computational Chemistry
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The reaction of N-allyl-N-(2-halobenzyl)-acetamides and derivatives was investigated in liquid ammonia under irradiation with the nucleophiles Me3Sn−, Ph2P− and O2NCH2 −. Following this procedure, novel substituted 2- acetyl-1,2,3,4-tetrahydroisoquinolines and substituted 2-acetyl- 2,3,4,5-tetrahydro-1H-benzo[c]azepines were obtained in good yields. These reactions are proposed to occur through the intermediacy of aryl radicals, which by intramolecular 6-exo or 7-endo attack to a double bond cyclize to give aliphatic radicals, which react along the propagation steps of the SRN1 chain cycle to afford the cyclic substituted compounds as main products. The reactions were modeled with DFT methods, which provide a rational understanding that relates the product distribution to the structure of the aliphatic radicals proposed as intermediates and the kinetic of their formation.
Fil: Peisino, Lucas Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Pierini, Adriana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The reaction of N-allyl-N-(2-halobenzyl)-acetamides and derivatives was investigated in liquid ammonia under irradiation with the nucleophiles Me3Sn−, Ph2P− and O2NCH2 −. Following this procedure, novel substituted 2- acetyl-1,2,3,4-tetrahydroisoquinolines and substituted 2-acetyl- 2,3,4,5-tetrahydro-1H-benzo[c]azepines were obtained in good yields. These reactions are proposed to occur through the intermediacy of aryl radicals, which by intramolecular 6-exo or 7-endo attack to a double bond cyclize to give aliphatic radicals, which react along the propagation steps of the SRN1 chain cycle to afford the cyclic substituted compounds as main products. The reactions were modeled with DFT methods, which provide a rational understanding that relates the product distribution to the structure of the aliphatic radicals proposed as intermediates and the kinetic of their formation.
publishDate 2013
dc.date.none.fl_str_mv 2013-04
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/11336/25405
Peisino, Lucas Ernesto; Pierini, Adriana Beatriz; Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution; American Chemical Society; Journal of Organic Chemistry; 78; 10; 4-2013; 4719-4729
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/25405
identifier_str_mv Peisino, Lucas Ernesto; Pierini, Adriana Beatriz; Experimental and computational study of 6-exo and 7-endo cyclization of Aryl radicals followed by Tandem SRN1 substitution; American Chemical Society; Journal of Organic Chemistry; 78; 10; 4-2013; 4719-4729
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jo4001788
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jo4001788
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
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 13.22299

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