Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides

Autores
Porta, Exequiel Oscar Jesús; Vallejos, Margarita; Bracca, Andrea Beatriz Juana
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
[3,3]-Sigmatropic rearrangement of isoprenyl azides has been extensively investigated in an experimental and theoretical level. Prenylazides with different chain lengths and phenyl prenylazide have been synthesized. NMR analysis of each azide has been made to determine the equilibrium composition, showing the predominance of primary allyl azides over the tertiary ones and E over Z isomer, regardless of the chain length, temperature, solvent or the regiochemistry of the precursor isoprenyl alcohol. It was determined that phenyl prenylazides do not experience [3,3]-sigmatropic rearrangement. In order to rationalize the experimental results and to gain insight in the mechanism of the [3,3]-sigmatropic rearrangement of prenylazides a theoretical study was performed using density functional theory and the QTAIM approach.
Fil: Porta, Exequiel Oscar Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Bracca, Andrea Beatriz Juana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Materia
PRENYL AZIDES
SIGMATROPIC REARRANGEMENT
QTAIM
THEORETICAL STUDIES
QTAIM
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:11336/50747
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azidesPorta, Exequiel Oscar JesúsVallejos, MargaritaBracca, Andrea Beatriz JuanaPRENYL AZIDESSIGMATROPIC REARRANGEMENTQTAIMTHEORETICAL STUDIESQTAIMhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1[3,3]-Sigmatropic rearrangement of isoprenyl azides has been extensively investigated in an experimental and theoretical level. Prenylazides with different chain lengths and phenyl prenylazide have been synthesized. NMR analysis of each azide has been made to determine the equilibrium composition, showing the predominance of primary allyl azides over the tertiary ones and E over Z isomer, regardless of the chain length, temperature, solvent or the regiochemistry of the precursor isoprenyl alcohol. It was determined that phenyl prenylazides do not experience [3,3]-sigmatropic rearrangement. In order to rationalize the experimental results and to gain insight in the mechanism of the [3,3]-sigmatropic rearrangement of prenylazides a theoretical study was performed using density functional theory and the QTAIM approach.Fil: Porta, Exequiel Oscar Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Bracca, Andrea Beatriz Juana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaRoyal Society of Chemistry2017-10info: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/11336/50747Porta, Exequiel Oscar Jesús; Vallejos, Margarita; Bracca, Andrea Beatriz Juana; ; Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides; Royal Society of Chemistry; RSC Advances; 7; 75; 10-2017; 47527-475382046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2017/RA/C7RA09759J#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C7RA09759Jinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:24:09Zoai:ri.conicet.gov.ar:11336/50747instacron: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:34982025-09-10 13:24:10.068CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
title Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
spellingShingle Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
Porta, Exequiel Oscar Jesús
PRENYL AZIDES
SIGMATROPIC REARRANGEMENT
QTAIM
THEORETICAL STUDIES
QTAIM
title_short Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
title_full Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
title_fullStr Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
title_full_unstemmed Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
title_sort Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides
dc.creator.none.fl_str_mv Porta, Exequiel Oscar Jesús
Vallejos, Margarita
Bracca, Andrea Beatriz Juana
author Porta, Exequiel Oscar Jesús
author_facet Porta, Exequiel Oscar Jesús
Vallejos, Margarita
Bracca, Andrea Beatriz Juana
author_role author
author2 Vallejos, Margarita
Bracca, Andrea Beatriz Juana
author2_role author
author
dc.subject.none.fl_str_mv PRENYL AZIDES
SIGMATROPIC REARRANGEMENT
QTAIM
THEORETICAL STUDIES
QTAIM
topic PRENYL AZIDES
SIGMATROPIC REARRANGEMENT
QTAIM
THEORETICAL STUDIES
QTAIM
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv [3,3]-Sigmatropic rearrangement of isoprenyl azides has been extensively investigated in an experimental and theoretical level. Prenylazides with different chain lengths and phenyl prenylazide have been synthesized. NMR analysis of each azide has been made to determine the equilibrium composition, showing the predominance of primary allyl azides over the tertiary ones and E over Z isomer, regardless of the chain length, temperature, solvent or the regiochemistry of the precursor isoprenyl alcohol. It was determined that phenyl prenylazides do not experience [3,3]-sigmatropic rearrangement. In order to rationalize the experimental results and to gain insight in the mechanism of the [3,3]-sigmatropic rearrangement of prenylazides a theoretical study was performed using density functional theory and the QTAIM approach.
Fil: Porta, Exequiel Oscar Jesús. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Bracca, Andrea Beatriz Juana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
description [3,3]-Sigmatropic rearrangement of isoprenyl azides has been extensively investigated in an experimental and theoretical level. Prenylazides with different chain lengths and phenyl prenylazide have been synthesized. NMR analysis of each azide has been made to determine the equilibrium composition, showing the predominance of primary allyl azides over the tertiary ones and E over Z isomer, regardless of the chain length, temperature, solvent or the regiochemistry of the precursor isoprenyl alcohol. It was determined that phenyl prenylazides do not experience [3,3]-sigmatropic rearrangement. In order to rationalize the experimental results and to gain insight in the mechanism of the [3,3]-sigmatropic rearrangement of prenylazides a theoretical study was performed using density functional theory and the QTAIM approach.
publishDate 2017
dc.date.none.fl_str_mv 2017-10
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/11336/50747
Porta, Exequiel Oscar Jesús; Vallejos, Margarita; Bracca, Andrea Beatriz Juana; ; Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides; Royal Society of Chemistry; RSC Advances; 7; 75; 10-2017; 47527-47538
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/50747
identifier_str_mv Porta, Exequiel Oscar Jesús; Vallejos, Margarita; Bracca, Andrea Beatriz Juana; ; Experimental and theoretical studies of the [3,3]-sigmatropic rearrangement of prenyl azides; Royal Society of Chemistry; RSC Advances; 7; 75; 10-2017; 47527-47538
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
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info:eu-repo/semantics/altIdentifier/doi/10.1039/C7RA09759J
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.48226

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