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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/25415
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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 Técnicas2025-09-29T09:37:23Zoai: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:34982025-09-29 09:37:23.629CONICET 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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1844613177265881088 |
score |
13.070432 |