Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization

Autores
Romero Cordero, Ivan Exehomio; Vallejos, Margarita; Barata Vallejo, Sebastian; Bonesi, Sergio Mauricio; Postigo, Jose Alberto
Año de publicación
2025
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The acetone-sensitized [6π]-electrocyclization of unsubstituted, mono-, and disubstituted triarylamines (TAAs: substituents H, CH₃, CH₃O, Cl, CnF₂n+1; n=1, 3, 4, 6, 8, 10) under 310 nm light led to the formation of endo- and exo-carbazoles in high yields; particularly, TAAs substituted with inductive electron-withdrawing groups (Cl, CnF2n+1) exhibit remarkable endo-selectivity towards cyclization. For TAAs substituted with both inductive electron- withdrawing and donating groups, the photocyclization towards endo carbazoles is dictated by the presence of the electron-withdrawing groups. Chemical yields (%), quantum yields of conversion (φR), apparent cyclization rate constants (kcyc), and Hammett plots correlations are illustrated for all substituted TAAs in acetone. Photophysical studies reveal that TAAs substituted with resonance electron-withdrawing groups (OAc, NO2, CHO) do not undergo electrocyclization in acetone at 310 nm due to formation of charge-transfer states that vastly deactivate the triplet reactive manifold, paralleling the behavior observed in MeCN as solvent. Absorption and emission spectra, Stokes shifts, and singlet excited state energies are illustrated for substituted TAAs and carbazoles. In-silico studies support the high stereoselectivity observed for the preferred endo- photosensitized [6π]-electrocyclization of Cl- and perfluoroalkyl-substituted TAAs.
Fil: Romero Cordero, Ivan Exehomio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
PHOTOSENSITIZED ELECTROCYCLIZATION
CARBAZOLE SYNTHESIS
COMPUTATIONAL PHOTOCHEMISTRY
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:11336/273062
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the PhotocyclizationRomero Cordero, Ivan ExehomioVallejos, MargaritaBarata Vallejo, SebastianBonesi, Sergio MauricioPostigo, Jose AlbertoPHOTOSENSITIZED ELECTROCYCLIZATIONCARBAZOLE SYNTHESISCOMPUTATIONAL PHOTOCHEMISTRYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The acetone-sensitized [6π]-electrocyclization of unsubstituted, mono-, and disubstituted triarylamines (TAAs: substituents H, CH₃, CH₃O, Cl, CnF₂n+1; n=1, 3, 4, 6, 8, 10) under 310 nm light led to the formation of endo- and exo-carbazoles in high yields; particularly, TAAs substituted with inductive electron-withdrawing groups (Cl, CnF2n+1) exhibit remarkable endo-selectivity towards cyclization. For TAAs substituted with both inductive electron- withdrawing and donating groups, the photocyclization towards endo carbazoles is dictated by the presence of the electron-withdrawing groups. Chemical yields (%), quantum yields of conversion (φR), apparent cyclization rate constants (kcyc), and Hammett plots correlations are illustrated for all substituted TAAs in acetone. Photophysical studies reveal that TAAs substituted with resonance electron-withdrawing groups (OAc, NO2, CHO) do not undergo electrocyclization in acetone at 310 nm due to formation of charge-transfer states that vastly deactivate the triplet reactive manifold, paralleling the behavior observed in MeCN as solvent. Absorption and emission spectra, Stokes shifts, and singlet excited state energies are illustrated for substituted TAAs and carbazoles. In-silico studies support the high stereoselectivity observed for the preferred endo- photosensitized [6π]-electrocyclization of Cl- and perfluoroalkyl-substituted TAAs.Fil: Romero Cordero, Ivan Exehomio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaWiley VCH Verlag2025-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/273062Romero Cordero, Ivan Exehomio; Vallejos, Margarita; Barata Vallejo, Sebastian; Bonesi, Sergio Mauricio; Postigo, Jose Alberto; Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization; Wiley VCH Verlag; Chemistry- A European Journal; 31; 22; 2-2025; 1-160947-6539CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202500133info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202500133info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:20:21Zoai:ri.conicet.gov.ar:11336/273062instacron: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 11:20:21.97CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
title Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
spellingShingle Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
Romero Cordero, Ivan Exehomio
PHOTOSENSITIZED ELECTROCYCLIZATION
CARBAZOLE SYNTHESIS
COMPUTATIONAL PHOTOCHEMISTRY
title_short Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
title_full Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
title_fullStr Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
title_full_unstemmed Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
title_sort Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization
dc.creator.none.fl_str_mv Romero Cordero, Ivan Exehomio
Vallejos, Margarita
Barata Vallejo, Sebastian
Bonesi, Sergio Mauricio
Postigo, Jose Alberto
author Romero Cordero, Ivan Exehomio
author_facet Romero Cordero, Ivan Exehomio
Vallejos, Margarita
Barata Vallejo, Sebastian
Bonesi, Sergio Mauricio
Postigo, Jose Alberto
author_role author
author2 Vallejos, Margarita
Barata Vallejo, Sebastian
Bonesi, Sergio Mauricio
Postigo, Jose Alberto
author2_role author
author
author
author
dc.subject.none.fl_str_mv PHOTOSENSITIZED ELECTROCYCLIZATION
CARBAZOLE SYNTHESIS
COMPUTATIONAL PHOTOCHEMISTRY
topic PHOTOSENSITIZED ELECTROCYCLIZATION
CARBAZOLE SYNTHESIS
COMPUTATIONAL PHOTOCHEMISTRY
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 acetone-sensitized [6π]-electrocyclization of unsubstituted, mono-, and disubstituted triarylamines (TAAs: substituents H, CH₃, CH₃O, Cl, CnF₂n+1; n=1, 3, 4, 6, 8, 10) under 310 nm light led to the formation of endo- and exo-carbazoles in high yields; particularly, TAAs substituted with inductive electron-withdrawing groups (Cl, CnF2n+1) exhibit remarkable endo-selectivity towards cyclization. For TAAs substituted with both inductive electron- withdrawing and donating groups, the photocyclization towards endo carbazoles is dictated by the presence of the electron-withdrawing groups. Chemical yields (%), quantum yields of conversion (φR), apparent cyclization rate constants (kcyc), and Hammett plots correlations are illustrated for all substituted TAAs in acetone. Photophysical studies reveal that TAAs substituted with resonance electron-withdrawing groups (OAc, NO2, CHO) do not undergo electrocyclization in acetone at 310 nm due to formation of charge-transfer states that vastly deactivate the triplet reactive manifold, paralleling the behavior observed in MeCN as solvent. Absorption and emission spectra, Stokes shifts, and singlet excited state energies are illustrated for substituted TAAs and carbazoles. In-silico studies support the high stereoselectivity observed for the preferred endo- photosensitized [6π]-electrocyclization of Cl- and perfluoroalkyl-substituted TAAs.
Fil: Romero Cordero, Ivan Exehomio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Vallejos, Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentina
Fil: Barata Vallejo, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Postigo, Jose Alberto. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description The acetone-sensitized [6π]-electrocyclization of unsubstituted, mono-, and disubstituted triarylamines (TAAs: substituents H, CH₃, CH₃O, Cl, CnF₂n+1; n=1, 3, 4, 6, 8, 10) under 310 nm light led to the formation of endo- and exo-carbazoles in high yields; particularly, TAAs substituted with inductive electron-withdrawing groups (Cl, CnF2n+1) exhibit remarkable endo-selectivity towards cyclization. For TAAs substituted with both inductive electron- withdrawing and donating groups, the photocyclization towards endo carbazoles is dictated by the presence of the electron-withdrawing groups. Chemical yields (%), quantum yields of conversion (φR), apparent cyclization rate constants (kcyc), and Hammett plots correlations are illustrated for all substituted TAAs in acetone. Photophysical studies reveal that TAAs substituted with resonance electron-withdrawing groups (OAc, NO2, CHO) do not undergo electrocyclization in acetone at 310 nm due to formation of charge-transfer states that vastly deactivate the triplet reactive manifold, paralleling the behavior observed in MeCN as solvent. Absorption and emission spectra, Stokes shifts, and singlet excited state energies are illustrated for substituted TAAs and carbazoles. In-silico studies support the high stereoselectivity observed for the preferred endo- photosensitized [6π]-electrocyclization of Cl- and perfluoroalkyl-substituted TAAs.
publishDate 2025
dc.date.none.fl_str_mv 2025-02
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/11336/273062
Romero Cordero, Ivan Exehomio; Vallejos, Margarita; Barata Vallejo, Sebastian; Bonesi, Sergio Mauricio; Postigo, Jose Alberto; Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization; Wiley VCH Verlag; Chemistry- A European Journal; 31; 22; 2-2025; 1-16
0947-6539
CONICET Digital
CONICET
url http://hdl.handle.net/11336/273062
identifier_str_mv Romero Cordero, Ivan Exehomio; Vallejos, Margarita; Barata Vallejo, Sebastian; Bonesi, Sergio Mauricio; Postigo, Jose Alberto; Syntheses of Carbazoles by Photosensitized Electrocyclization of Triarylamines. Effect of Inductive Electron‐Withdrawing Groups on the Photocyclization; Wiley VCH Verlag; Chemistry- A European Journal; 31; 22; 2-2025; 1-16
0947-6539
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202500133
info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202500133
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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
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dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
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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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