Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids

Autores
Camargo Solorzano, Gloria Patricia; Baumgartner, Maria Teresa del V.; Puiatti, Marcelo; Jimenez, Liliana Beatriz
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Perylene and its derivatives are some of the most interesting chromophores in the field of molecular design. One of the most employed methodologies for their synthesis is the cyclodehydrogenation of binaphthyls mediated by Lewis acids. In this article, we investigated the cyclodehydrogenation reaction of 2-substituted binaphthyls to afford thebay-substituted perylene. By using AlCl3as a Lewis acid and high temperatures (the Scholl reaction), two new products bearing NH2and N(CH3)2groups at position 2 of the perylene ring were synthesized. Under these conditions, we were also able to obtain terrylene from ternaphthalene in 38% yield after two cyclodehydrogenation reactions in a single step. The attempts to promote the formation of a radical cation (necessary intermediary for the oxidative aromatic coupling mechanism) by using FeCl3or a strong oxidant like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) did not yield the expected products. DFT calculations suggested that the lack of reaction for oxidative aromatic coupling is caused by the difference between the oxidation potentials of the donor/acceptor couple. In the case of the Scholl reaction, the regiochemistry involved in the formation of the σ-complex together with the activation energy of the C-C coupling reaction helped to explain the differences in the reactivity of the different substrates studied.
Fil: Camargo Solorzano, Gloria Patricia. 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
Fil: Baumgartner, Maria Teresa del V.. 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
Fil: Puiatti, Marcelo. 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
Fil: Jimenez, Liliana Beatriz. 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
Cyclodehydrogenation
Arenium cation
Radical cation
Perylene
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:11336/144353
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acidsCamargo Solorzano, Gloria PatriciaBaumgartner, Maria Teresa del V.Puiatti, MarceloJimenez, Liliana BeatrizCyclodehydrogenationArenium cationRadical cationPerylenehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Perylene and its derivatives are some of the most interesting chromophores in the field of molecular design. One of the most employed methodologies for their synthesis is the cyclodehydrogenation of binaphthyls mediated by Lewis acids. In this article, we investigated the cyclodehydrogenation reaction of 2-substituted binaphthyls to afford thebay-substituted perylene. By using AlCl3as a Lewis acid and high temperatures (the Scholl reaction), two new products bearing NH2and N(CH3)2groups at position 2 of the perylene ring were synthesized. Under these conditions, we were also able to obtain terrylene from ternaphthalene in 38% yield after two cyclodehydrogenation reactions in a single step. The attempts to promote the formation of a radical cation (necessary intermediary for the oxidative aromatic coupling mechanism) by using FeCl3or a strong oxidant like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) did not yield the expected products. DFT calculations suggested that the lack of reaction for oxidative aromatic coupling is caused by the difference between the oxidation potentials of the donor/acceptor couple. In the case of the Scholl reaction, the regiochemistry involved in the formation of the σ-complex together with the activation energy of the C-C coupling reaction helped to explain the differences in the reactivity of the different substrates studied.Fil: Camargo Solorzano, Gloria Patricia. 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; ArgentinaFil: Baumgartner, Maria Teresa del V.. 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; ArgentinaFil: Puiatti, Marcelo. 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; ArgentinaFil: Jimenez, Liliana Beatriz. 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; ArgentinaRoyal Society of Chemistry2020-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/144353Camargo Solorzano, Gloria Patricia; Baumgartner, Maria Teresa del V.; Puiatti, Marcelo; Jimenez, Liliana Beatriz; Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids; Royal Society of Chemistry; RSC Advances; 10; 37; 6-2020; 1-122046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/D0RA04213Ginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/RA/D0RA04213Ginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:36:28Zoai:ri.conicet.gov.ar:11336/144353instacron: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 09:36:28.986CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
title Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
spellingShingle Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
Camargo Solorzano, Gloria Patricia
Cyclodehydrogenation
Arenium cation
Radical cation
Perylene
title_short Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
title_full Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
title_fullStr Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
title_full_unstemmed Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
title_sort Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids
dc.creator.none.fl_str_mv Camargo Solorzano, Gloria Patricia
Baumgartner, Maria Teresa del V.
Puiatti, Marcelo
Jimenez, Liliana Beatriz
author Camargo Solorzano, Gloria Patricia
author_facet Camargo Solorzano, Gloria Patricia
Baumgartner, Maria Teresa del V.
Puiatti, Marcelo
Jimenez, Liliana Beatriz
author_role author
author2 Baumgartner, Maria Teresa del V.
Puiatti, Marcelo
Jimenez, Liliana Beatriz
author2_role author
author
author
dc.subject.none.fl_str_mv Cyclodehydrogenation
Arenium cation
Radical cation
Perylene
topic Cyclodehydrogenation
Arenium cation
Radical cation
Perylene
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Perylene and its derivatives are some of the most interesting chromophores in the field of molecular design. One of the most employed methodologies for their synthesis is the cyclodehydrogenation of binaphthyls mediated by Lewis acids. In this article, we investigated the cyclodehydrogenation reaction of 2-substituted binaphthyls to afford thebay-substituted perylene. By using AlCl3as a Lewis acid and high temperatures (the Scholl reaction), two new products bearing NH2and N(CH3)2groups at position 2 of the perylene ring were synthesized. Under these conditions, we were also able to obtain terrylene from ternaphthalene in 38% yield after two cyclodehydrogenation reactions in a single step. The attempts to promote the formation of a radical cation (necessary intermediary for the oxidative aromatic coupling mechanism) by using FeCl3or a strong oxidant like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) did not yield the expected products. DFT calculations suggested that the lack of reaction for oxidative aromatic coupling is caused by the difference between the oxidation potentials of the donor/acceptor couple. In the case of the Scholl reaction, the regiochemistry involved in the formation of the σ-complex together with the activation energy of the C-C coupling reaction helped to explain the differences in the reactivity of the different substrates studied.
Fil: Camargo Solorzano, Gloria Patricia. 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
Fil: Baumgartner, Maria Teresa del V.. 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
Fil: Puiatti, Marcelo. 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
Fil: Jimenez, Liliana Beatriz. 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 Perylene and its derivatives are some of the most interesting chromophores in the field of molecular design. One of the most employed methodologies for their synthesis is the cyclodehydrogenation of binaphthyls mediated by Lewis acids. In this article, we investigated the cyclodehydrogenation reaction of 2-substituted binaphthyls to afford thebay-substituted perylene. By using AlCl3as a Lewis acid and high temperatures (the Scholl reaction), two new products bearing NH2and N(CH3)2groups at position 2 of the perylene ring were synthesized. Under these conditions, we were also able to obtain terrylene from ternaphthalene in 38% yield after two cyclodehydrogenation reactions in a single step. The attempts to promote the formation of a radical cation (necessary intermediary for the oxidative aromatic coupling mechanism) by using FeCl3or a strong oxidant like 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) did not yield the expected products. DFT calculations suggested that the lack of reaction for oxidative aromatic coupling is caused by the difference between the oxidation potentials of the donor/acceptor couple. In the case of the Scholl reaction, the regiochemistry involved in the formation of the σ-complex together with the activation energy of the C-C coupling reaction helped to explain the differences in the reactivity of the different substrates studied.
publishDate 2020
dc.date.none.fl_str_mv 2020-06
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/11336/144353
Camargo Solorzano, Gloria Patricia; Baumgartner, Maria Teresa del V.; Puiatti, Marcelo; Jimenez, Liliana Beatriz; Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids; Royal Society of Chemistry; RSC Advances; 10; 37; 6-2020; 1-12
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/144353
identifier_str_mv Camargo Solorzano, Gloria Patricia; Baumgartner, Maria Teresa del V.; Puiatti, Marcelo; Jimenez, Liliana Beatriz; Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids; Royal Society of Chemistry; RSC Advances; 10; 37; 6-2020; 1-12
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/D0RA04213G
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/RA/D0RA04213G
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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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
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.069144

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