Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide

Autores
Peláez, Walter José; Pinho e Melo, Teresa M.V.D.
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The generation and reactivity of 1-benzyl-5-trifluoromethyl-azafulvenium methide are described. Under microwave induced pyrolysis this intermediate could be trapped by dipolarophiles acting as a 4π as well as 8π dipole. It was observed that with dimethyl acetylenedicarboxylate the 1,3-dipolar cycloadduct was the major product whereas with N-substituted maleimides the major product results from the addition across the 1,7-position. FMO analysis of the cycloadditions corroborated the rationalization of the observed reactivity. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the stereoselectivity observed in the cycloaddition of 1-benzyl-5-trifluoromethyl-azafulvenium methide with N-substituted maleimides. The study revealed that exo-cycloaddition is the main reaction path for the 1,7-cycloaddition, while the endo-approach is the main mode of reaction leading to 1,3-cycloadducts. In addition, under flash vacuum pyrolysis or conventional thermolysis, 1-benzyl-5-trifluoromethyl-azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the efficient formation of 2-methyl-1-styryl-3-trifluoromethyl-1H-pyrrole.
Fil: Peláez, Walter José. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Pinho e Melo, Teresa M.V.D.. Universidad de Coimbra; Portugal
Materia
Cycloadditions
Dft Calculations
Flash Vacuum Pyrolysis
Trifluoromethylpyrroles
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/25415
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxidePeláez, Walter JoséPinho e Melo, Teresa M.V.D.CycloadditionsDft CalculationsFlash Vacuum PyrolysisTrifluoromethylpyrroleshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The generation and reactivity of 1-benzyl-5-trifluoromethyl-azafulvenium methide are described. Under microwave induced pyrolysis this intermediate could be trapped by dipolarophiles acting as a 4π as well as 8π dipole. It was observed that with dimethyl acetylenedicarboxylate the 1,3-dipolar cycloadduct was the major product whereas with N-substituted maleimides the major product results from the addition across the 1,7-position. FMO analysis of the cycloadditions corroborated the rationalization of the observed reactivity. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the stereoselectivity observed in the cycloaddition of 1-benzyl-5-trifluoromethyl-azafulvenium methide with N-substituted maleimides. The study revealed that exo-cycloaddition is the main reaction path for the 1,7-cycloaddition, while the endo-approach is the main mode of reaction leading to 1,3-cycloadducts. In addition, under flash vacuum pyrolysis or conventional thermolysis, 1-benzyl-5-trifluoromethyl-azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the efficient formation of 2-methyl-1-styryl-3-trifluoromethyl-1H-pyrrole.Fil: Peláez, Walter José. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Pinho e Melo, Teresa M.V.D.. Universidad de Coimbra; PortugalElsevier2013-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/25415Peláez, Walter José; Pinho e Melo, Teresa M.V.D.; Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide; Elsevier; Tetrahedron; 69; 18; 3-2013; 3646-36550040-4020CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.tet.2013.03.017info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0040402013003670info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:05:31Zoai:ri.conicet.gov.ar:11336/25415instacron: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:34982025-10-22 11:05:32.301CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
title Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
spellingShingle Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
Peláez, Walter José
Cycloadditions
Dft Calculations
Flash Vacuum Pyrolysis
Trifluoromethylpyrroles
title_short Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
title_full Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
title_fullStr Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
title_full_unstemmed Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
title_sort Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide
dc.creator.none.fl_str_mv Peláez, Walter José
Pinho e Melo, Teresa M.V.D.
author Peláez, Walter José
author_facet Peláez, Walter José
Pinho e Melo, Teresa M.V.D.
author_role author
author2 Pinho e Melo, Teresa M.V.D.
author2_role author
dc.subject.none.fl_str_mv Cycloadditions
Dft Calculations
Flash Vacuum Pyrolysis
Trifluoromethylpyrroles
topic Cycloadditions
Dft Calculations
Flash Vacuum Pyrolysis
Trifluoromethylpyrroles
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 1-benzyl-5-trifluoromethyl-azafulvenium methide are described. Under microwave induced pyrolysis this intermediate could be trapped by dipolarophiles acting as a 4π as well as 8π dipole. It was observed that with dimethyl acetylenedicarboxylate the 1,3-dipolar cycloadduct was the major product whereas with N-substituted maleimides the major product results from the addition across the 1,7-position. FMO analysis of the cycloadditions corroborated the rationalization of the observed reactivity. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the stereoselectivity observed in the cycloaddition of 1-benzyl-5-trifluoromethyl-azafulvenium methide with N-substituted maleimides. The study revealed that exo-cycloaddition is the main reaction path for the 1,7-cycloaddition, while the endo-approach is the main mode of reaction leading to 1,3-cycloadducts. In addition, under flash vacuum pyrolysis or conventional thermolysis, 1-benzyl-5-trifluoromethyl-azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the efficient formation of 2-methyl-1-styryl-3-trifluoromethyl-1H-pyrrole.
Fil: Peláez, Walter José. Universidad de Coimbra; Portugal. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Pinho e Melo, Teresa M.V.D.. Universidad de Coimbra; Portugal
description The generation and reactivity of 1-benzyl-5-trifluoromethyl-azafulvenium methide are described. Under microwave induced pyrolysis this intermediate could be trapped by dipolarophiles acting as a 4π as well as 8π dipole. It was observed that with dimethyl acetylenedicarboxylate the 1,3-dipolar cycloadduct was the major product whereas with N-substituted maleimides the major product results from the addition across the 1,7-position. FMO analysis of the cycloadditions corroborated the rationalization of the observed reactivity. Quantum chemical calculations carried out at the DFT level of theory allowed the rationalization of the stereoselectivity observed in the cycloaddition of 1-benzyl-5-trifluoromethyl-azafulvenium methide with N-substituted maleimides. The study revealed that exo-cycloaddition is the main reaction path for the 1,7-cycloaddition, while the endo-approach is the main mode of reaction leading to 1,3-cycloadducts. In addition, under flash vacuum pyrolysis or conventional thermolysis, 1-benzyl-5-trifluoromethyl-azafulvenium methide undergoes an allowed suprafacial sigmatropic [1,8]H shift leading to the efficient formation of 2-methyl-1-styryl-3-trifluoromethyl-1H-pyrrole.
publishDate 2013
dc.date.none.fl_str_mv 2013-03
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/11336/25415
Peláez, Walter José; Pinho e Melo, Teresa M.V.D.; Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide; Elsevier; Tetrahedron; 69; 18; 3-2013; 3646-3655
0040-4020
CONICET Digital
CONICET
url http://hdl.handle.net/11336/25415
identifier_str_mv Peláez, Walter José; Pinho e Melo, Teresa M.V.D.; Synthesis and thermal reactivity of 3-benzyl-7-trifluoromethyl-1H,3H-pyrrolo[1,2-c]thiazole-2,2-dioxide; Elsevier; Tetrahedron; 69; 18; 3-2013; 3646-3655
0040-4020
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.tet.2013.03.017
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0040402013003670
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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 12.982451

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