1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions

Autores
Argüello, Gustavo Alejandro
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The generation and reactivity of a new 1-methyl-5-(trifluoromethyl)azafulvenium methide are described. Under microwave-induced pyrolysis conditions this intermediate could be trapped by dipolarophiles, acting either as a 4π or as an 8π dipole. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the results observed in the cycloaddition of 1-methyl-5-(trifluoromethyl)azafulvenium methide and N-substituted maleimides. The study revealed that for 1,7-cycloadducts the major products are obtained in the trans configuration through the unusual exo-cycloaddition mode, whereas for 1,3-cycloadducts the cis counterparts are obtained from this unexpected approach. In addition, under flash vacuum pyrolysis or conventional thermolysis conditions 1-methyl-5-(trifluoromethyl)azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the formation of 2-methyl-3-(trifluoromethyl)-1-vinyl-1H-pyrrole.
Fil: Argüello, Gustavo Alejandro. 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
Cycloaddition
Configuration Determination
Sigmatropic Rearrangement
Flash Pyrolysis
Microwavechemistry
Density Functional Calculations
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:11336/31234
Acceder
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network_name_str CONICET Digital (CONICET)
spelling 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-CycloadditionsArgüello, Gustavo AlejandroCycloadditionConfiguration DeterminationSigmatropic RearrangementFlash PyrolysisMicrowavechemistryDensity Functional Calculationshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The generation and reactivity of a new 1-methyl-5-(trifluoromethyl)azafulvenium methide are described. Under microwave-induced pyrolysis conditions this intermediate could be trapped by dipolarophiles, acting either as a 4π or as an 8π dipole. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the results observed in the cycloaddition of 1-methyl-5-(trifluoromethyl)azafulvenium methide and N-substituted maleimides. The study revealed that for 1,7-cycloadducts the major products are obtained in the trans configuration through the unusual exo-cycloaddition mode, whereas for 1,3-cycloadducts the cis counterparts are obtained from this unexpected approach. In addition, under flash vacuum pyrolysis or conventional thermolysis conditions 1-methyl-5-(trifluoromethyl)azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the formation of 2-methyl-3-(trifluoromethyl)-1-vinyl-1H-pyrrole.Fil: Argüello, Gustavo Alejandro. 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; ArgentinaWiley VCH Verlag2014-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31234Argüello, Gustavo Alejandro; 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions; Wiley VCH Verlag; European Journal of Organic Chemistry; 14; 6-2014; 2933-29411434-193XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1002/ejoc.201301922info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201301922/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 Técnicas2025-09-29T09:55:23Zoai:ri.conicet.gov.ar:11336/31234instacron: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 09:55:23.694CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
title 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
spellingShingle 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
Argüello, Gustavo Alejandro
Cycloaddition
Configuration Determination
Sigmatropic Rearrangement
Flash Pyrolysis
Microwavechemistry
Density Functional Calculations
title_short 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
title_full 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
title_fullStr 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
title_full_unstemmed 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
title_sort 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions
dc.creator.none.fl_str_mv Argüello, Gustavo Alejandro
author Argüello, Gustavo Alejandro
author_facet Argüello, Gustavo Alejandro
author_role author
dc.subject.none.fl_str_mv Cycloaddition
Configuration Determination
Sigmatropic Rearrangement
Flash Pyrolysis
Microwavechemistry
Density Functional Calculations
topic Cycloaddition
Configuration Determination
Sigmatropic Rearrangement
Flash Pyrolysis
Microwavechemistry
Density Functional Calculations
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 generation and reactivity of a new 1-methyl-5-(trifluoromethyl)azafulvenium methide are described. Under microwave-induced pyrolysis conditions this intermediate could be trapped by dipolarophiles, acting either as a 4π or as an 8π dipole. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the results observed in the cycloaddition of 1-methyl-5-(trifluoromethyl)azafulvenium methide and N-substituted maleimides. The study revealed that for 1,7-cycloadducts the major products are obtained in the trans configuration through the unusual exo-cycloaddition mode, whereas for 1,3-cycloadducts the cis counterparts are obtained from this unexpected approach. In addition, under flash vacuum pyrolysis or conventional thermolysis conditions 1-methyl-5-(trifluoromethyl)azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the formation of 2-methyl-3-(trifluoromethyl)-1-vinyl-1H-pyrrole.
Fil: Argüello, Gustavo Alejandro. 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 generation and reactivity of a new 1-methyl-5-(trifluoromethyl)azafulvenium methide are described. Under microwave-induced pyrolysis conditions this intermediate could be trapped by dipolarophiles, acting either as a 4π or as an 8π dipole. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the results observed in the cycloaddition of 1-methyl-5-(trifluoromethyl)azafulvenium methide and N-substituted maleimides. The study revealed that for 1,7-cycloadducts the major products are obtained in the trans configuration through the unusual exo-cycloaddition mode, whereas for 1,3-cycloadducts the cis counterparts are obtained from this unexpected approach. In addition, under flash vacuum pyrolysis or conventional thermolysis conditions 1-methyl-5-(trifluoromethyl)azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the formation of 2-methyl-3-(trifluoromethyl)-1-vinyl-1H-pyrrole.
publishDate 2014
dc.date.none.fl_str_mv 2014-06
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/11336/31234
Argüello, Gustavo Alejandro; 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions; Wiley VCH Verlag; European Journal of Organic Chemistry; 14; 6-2014; 2933-2941
1434-193X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31234
identifier_str_mv Argüello, Gustavo Alejandro; 1-Methyl-5-(trifluoromethyl)azafulvenium Methide, an Intermediate ThatUndergoes Reaction through “Unusual”cis-exo-1,3- andtrans-exo-1,7-Cycloadditions; Wiley VCH Verlag; European Journal of Organic Chemistry; 14; 6-2014; 2933-2941
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.201301922
info:eu-repo/semantics/altIdentifier/url/http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201301922/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
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
_version_ 1844613670417465344
score 13.070432

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