One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones

Autores
Pis Diez, Cristian Manuel; Fernández, Julián Francisco; Di Venosa, Gabriela Mariana; Casas, Adriana Gabriela; Pis Diez, Reinaldo; Palermo, Jorge Alejandro
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A series of novel 1-(N-indolyl)-1,3-butadienes, as (1 : 1) mixtures of the (E) and (Z) dienes, was prepared in one step by base-catalysed isomerization of N-alkylindoles with a terminal butyne chain. The reaction conditions are mild, and in all cases the yields were very high (>90%). The (E) and (Z) dienes were separable by preparative TLC and could be fully characterized. This isomerization proceeded readily in the case of a butynyl chain, but didn't take place with a pentynyl chain. A mechanism was proposed for this reaction, based on previous studies on the isomerization of alkynes in basic media, and a key intermediate that supports the proposed mechanism could be isolated and fully characterized. A theoretical study of the proposed mechanism was performed by computational methods and the results validated the proposal. The reactivity of the synthesized dienes was studied in Diels–Alder reactions with p-benzoquinone, to obtain a small library of new 5-(N-indolyl)-1,4-naphthoquinones.The lack of reactivity in the case of the (Z) isomers was explained by calculation of the rotational curves of the central bond of the (Z) and (E) dienes. Finally, the cytotoxicity of the new 5-(N-indolyl)-1,4-naphthoquinones was tested against a panel of three cell lines.
Facultad de Ciencias Exactas
Centro de Química Inorgánica
Materia
Ciencias Exactas
Química
base-catalysed isomerization
reactivity
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc/3.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/104697

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spelling One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinonesPis Diez, Cristian ManuelFernández, Julián FranciscoDi Venosa, Gabriela MarianaCasas, Adriana GabrielaPis Diez, ReinaldoPalermo, Jorge AlejandroCiencias ExactasQuímicabase-catalysed isomerizationreactivityA series of novel 1-(N-indolyl)-1,3-butadienes, as (1 : 1) mixtures of the (E) and (Z) dienes, was prepared in one step by base-catalysed isomerization of N-alkylindoles with a terminal butyne chain. The reaction conditions are mild, and in all cases the yields were very high (>90%). The (E) and (Z) dienes were separable by preparative TLC and could be fully characterized. This isomerization proceeded readily in the case of a butynyl chain, but didn't take place with a pentynyl chain. A mechanism was proposed for this reaction, based on previous studies on the isomerization of alkynes in basic media, and a key intermediate that supports the proposed mechanism could be isolated and fully characterized. A theoretical study of the proposed mechanism was performed by computational methods and the results validated the proposal. The reactivity of the synthesized dienes was studied in Diels–Alder reactions with p-benzoquinone, to obtain a small library of new 5-(N-indolyl)-1,4-naphthoquinones.The lack of reactivity in the case of the (Z) isomers was explained by calculation of the rotational curves of the central bond of the (Z) and (E) dienes. Finally, the cytotoxicity of the new 5-(N-indolyl)-1,4-naphthoquinones was tested against a panel of three cell lines.Facultad de Ciencias ExactasCentro de Química Inorgánica2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf35998-36006http://sedici.unlp.edu.ar/handle/10915/104697enginfo:eu-repo/semantics/altIdentifier/url/http://hdl.handle.net/11336/95771info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/RA/C8RA05208Einfo:eu-repo/semantics/altIdentifier/issn/2046-2069info:eu-repo/semantics/altIdentifier/doi/10.1039/c8ra05208einfo:eu-repo/semantics/altIdentifier/hdl/11336/95771info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc/3.0/Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:22:47Zoai:sedici.unlp.edu.ar:10915/104697Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:22:48.156SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
title One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
spellingShingle One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
Pis Diez, Cristian Manuel
Ciencias Exactas
Química
base-catalysed isomerization
reactivity
title_short One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
title_full One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
title_fullStr One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
title_full_unstemmed One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
title_sort One-step preparation of novel 1-(N-indolyl)-1,3-butadienes by base-catalysed isomerization of alkynes as an access to 5-(N-indolyl)-naphthoquinones
dc.creator.none.fl_str_mv Pis Diez, Cristian Manuel
Fernández, Julián Francisco
Di Venosa, Gabriela Mariana
Casas, Adriana Gabriela
Pis Diez, Reinaldo
Palermo, Jorge Alejandro
author Pis Diez, Cristian Manuel
author_facet Pis Diez, Cristian Manuel
Fernández, Julián Francisco
Di Venosa, Gabriela Mariana
Casas, Adriana Gabriela
Pis Diez, Reinaldo
Palermo, Jorge Alejandro
author_role author
author2 Fernández, Julián Francisco
Di Venosa, Gabriela Mariana
Casas, Adriana Gabriela
Pis Diez, Reinaldo
Palermo, Jorge Alejandro
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Ciencias Exactas
Química
base-catalysed isomerization
reactivity
topic Ciencias Exactas
Química
base-catalysed isomerization
reactivity
dc.description.none.fl_txt_mv A series of novel 1-(N-indolyl)-1,3-butadienes, as (1 : 1) mixtures of the (E) and (Z) dienes, was prepared in one step by base-catalysed isomerization of N-alkylindoles with a terminal butyne chain. The reaction conditions are mild, and in all cases the yields were very high (>90%). The (E) and (Z) dienes were separable by preparative TLC and could be fully characterized. This isomerization proceeded readily in the case of a butynyl chain, but didn't take place with a pentynyl chain. A mechanism was proposed for this reaction, based on previous studies on the isomerization of alkynes in basic media, and a key intermediate that supports the proposed mechanism could be isolated and fully characterized. A theoretical study of the proposed mechanism was performed by computational methods and the results validated the proposal. The reactivity of the synthesized dienes was studied in Diels–Alder reactions with p-benzoquinone, to obtain a small library of new 5-(N-indolyl)-1,4-naphthoquinones.The lack of reactivity in the case of the (Z) isomers was explained by calculation of the rotational curves of the central bond of the (Z) and (E) dienes. Finally, the cytotoxicity of the new 5-(N-indolyl)-1,4-naphthoquinones was tested against a panel of three cell lines.
Facultad de Ciencias Exactas
Centro de Química Inorgánica
description A series of novel 1-(N-indolyl)-1,3-butadienes, as (1 : 1) mixtures of the (E) and (Z) dienes, was prepared in one step by base-catalysed isomerization of N-alkylindoles with a terminal butyne chain. The reaction conditions are mild, and in all cases the yields were very high (>90%). The (E) and (Z) dienes were separable by preparative TLC and could be fully characterized. This isomerization proceeded readily in the case of a butynyl chain, but didn't take place with a pentynyl chain. A mechanism was proposed for this reaction, based on previous studies on the isomerization of alkynes in basic media, and a key intermediate that supports the proposed mechanism could be isolated and fully characterized. A theoretical study of the proposed mechanism was performed by computational methods and the results validated the proposal. The reactivity of the synthesized dienes was studied in Diels–Alder reactions with p-benzoquinone, to obtain a small library of new 5-(N-indolyl)-1,4-naphthoquinones.The lack of reactivity in the case of the (Z) isomers was explained by calculation of the rotational curves of the central bond of the (Z) and (E) dienes. Finally, the cytotoxicity of the new 5-(N-indolyl)-1,4-naphthoquinones was tested against a panel of three cell lines.
publishDate 2018
dc.date.none.fl_str_mv 2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/104697
url http://sedici.unlp.edu.ar/handle/10915/104697
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://hdl.handle.net/11336/95771
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/RA/C8RA05208E
info:eu-repo/semantics/altIdentifier/issn/2046-2069
info:eu-repo/semantics/altIdentifier/doi/10.1039/c8ra05208e
info:eu-repo/semantics/altIdentifier/hdl/11336/95771
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc/3.0/
Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc/3.0/
Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0)
dc.format.none.fl_str_mv application/pdf
35998-36006
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
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repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
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