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

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...

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Autores principales: Pis Diez, C.M., Fernandez, J.F., Di Venosa, G., Casas, A., Pis Diez, R., Palermo, J.A.
Formato: JOUR
Materias:
Catalysis
Cell culture
Chains
Isomerization
Ketones
Olefins
Reaction intermediates
Basic media
Cell lines
Diels-Alder reaction
Naphthoquinones
P-benzoquinone
Reaction conditions
Theoretical study
Isomers
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_20462069_v8_n63_p35998_PisDiez
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_20462069_v8_n63_p35998_PisDiez
record_format dspace
spelling todo:paper_20462069_v8_n63_p35998_PisDiez2023-10-03T16:38:40Z 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, C.M. Fernandez, J.F. Di Venosa, G. Casas, A. Pis Diez, R. Palermo, J.A. Catalysis Cell culture Chains Isomerization Ketones Olefins Reaction intermediates Basic media Cell lines Diels-Alder reaction Naphthoquinones P-benzoquinone Reaction conditions Theoretical study Isomers 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. © 2018 The Royal Society of Chemistry. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_20462069_v8_n63_p35998_PisDiez
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Catalysis
Cell culture
Chains
Isomerization
Ketones
Olefins
Reaction intermediates
Basic media
Cell lines
Diels-Alder reaction
Naphthoquinones
P-benzoquinone
Reaction conditions
Theoretical study
Isomers
spellingShingle Catalysis
Cell culture
Chains
Isomerization
Ketones
Olefins
Reaction intermediates
Basic media
Cell lines
Diels-Alder reaction
Naphthoquinones
P-benzoquinone
Reaction conditions
Theoretical study
Isomers
Pis Diez, C.M.
Fernandez, J.F.
Di Venosa, G.
Casas, A.
Pis Diez, R.
Palermo, J.A.
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
topic_facet Catalysis
Cell culture
Chains
Isomerization
Ketones
Olefins
Reaction intermediates
Basic media
Cell lines
Diels-Alder reaction
Naphthoquinones
P-benzoquinone
Reaction conditions
Theoretical study
Isomers
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. © 2018 The Royal Society of Chemistry.
format JOUR
author Pis Diez, C.M.
Fernandez, J.F.
Di Venosa, G.
Casas, A.
Pis Diez, R.
Palermo, J.A.
author_facet Pis Diez, C.M.
Fernandez, J.F.
Di Venosa, G.
Casas, A.
Pis Diez, R.
Palermo, J.A.
author_sort Pis Diez, C.M.
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
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
url http://hdl.handle.net/20.500.12110/paper_20462069_v8_n63_p35998_PisDiez
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