Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group

Autores
Oksdath Mansilla, Gabriela; Hajj, Viviane; Andrada, Diego Marcelo; Argüello, Juan Elias; Bonin, Julien; Robert, Marc; Peñeñory, Alicia Beatriz
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Photodeprotection of 1,3-dithianes in the presence of thiapyrylium was performed to return to the parent carbonyl compound, and the mechanism was studied by steady state photolysis, laser flash photolysis, and theoretical calculations. Electron transfer from dithianes to triplet sensitizers is extremely fast, and the decay of dithiane radical cations was not affected by the presence of water or oxygen as the consequence of a favorable unimolecular fragmentation pathway. Similar behaviors were observed for dithianes bearing electron-releasing or electron-withdrawing substituents on the aryl moiety, evidenced by C−S bond cleavage to form a distonic radical cation species. The lack of reaction under nitrogen atmosphere, requirement of oxygen for good conversion yields, inhibition of the photodeprotection process by the presence of pbenzoquinone, and absence of a labeled carbonyl final product when the reaction is performed in the presence of H2 18O all suggest that the superoxide anion drives the deprotection reaction. Density functional theory computational studies on the reactions with water, molecular oxygen, and the superoxide radical anion support the experimental findings.
Fil: Oksdath Mansilla, Gabriela. 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: Hajj, Viviane. Université Paris Diderot - Paris 7; Francia
Fil: Andrada, Diego Marcelo. Philipps-Universität Marburg; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Argüello, Juan Elias. 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: Bonin, Julien. Université Paris Diderot - Paris 7; Francia
Fil: Robert, Marc. Université Paris Diderot - Paris 7; Francia
Fil: Peñeñory, Alicia 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
Photochemistry
Carbonyl Groups
Radical Cation
Dithiane
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:11336/43437
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/43437
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl GroupOksdath Mansilla, GabrielaHajj, VivianeAndrada, Diego MarceloArgüello, Juan EliasBonin, JulienRobert, MarcPeñeñory, Alicia BeatrizPhotochemistryCarbonyl GroupsRadical CationDithianehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Photodeprotection of 1,3-dithianes in the presence of thiapyrylium was performed to return to the parent carbonyl compound, and the mechanism was studied by steady state photolysis, laser flash photolysis, and theoretical calculations. Electron transfer from dithianes to triplet sensitizers is extremely fast, and the decay of dithiane radical cations was not affected by the presence of water or oxygen as the consequence of a favorable unimolecular fragmentation pathway. Similar behaviors were observed for dithianes bearing electron-releasing or electron-withdrawing substituents on the aryl moiety, evidenced by C−S bond cleavage to form a distonic radical cation species. The lack of reaction under nitrogen atmosphere, requirement of oxygen for good conversion yields, inhibition of the photodeprotection process by the presence of pbenzoquinone, and absence of a labeled carbonyl final product when the reaction is performed in the presence of H2 18O all suggest that the superoxide anion drives the deprotection reaction. Density functional theory computational studies on the reactions with water, molecular oxygen, and the superoxide radical anion support the experimental findings.Fil: Oksdath Mansilla, Gabriela. 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: Hajj, Viviane. Université Paris Diderot - Paris 7; FranciaFil: Andrada, Diego Marcelo. Philipps-Universität Marburg; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Argüello, Juan Elias. 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: Bonin, Julien. Université Paris Diderot - Paris 7; FranciaFil: Robert, Marc. Université Paris Diderot - Paris 7; FranciaFil: Peñeñory, Alicia 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; ArgentinaAmerican Chemical Society2015-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/43437Oksdath Mansilla, Gabriela; Hajj, Viviane; Andrada, Diego Marcelo; Argüello, Juan Elias; Bonin, Julien; et al.; Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group; American Chemical Society; Journal of Organic Chemistry; 80; 5; 2-2015; 2733-27390022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo502953tinfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo502953tinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:07:39Zoai:ri.conicet.gov.ar:11336/43437instacron: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 10:07:40.143CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
title Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
spellingShingle Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
Oksdath Mansilla, Gabriela
Photochemistry
Carbonyl Groups
Radical Cation
Dithiane
title_short Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
title_full Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
title_fullStr Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
title_full_unstemmed Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
title_sort Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group
dc.creator.none.fl_str_mv Oksdath Mansilla, Gabriela
Hajj, Viviane
Andrada, Diego Marcelo
Argüello, Juan Elias
Bonin, Julien
Robert, Marc
Peñeñory, Alicia Beatriz
author Oksdath Mansilla, Gabriela
author_facet Oksdath Mansilla, Gabriela
Hajj, Viviane
Andrada, Diego Marcelo
Argüello, Juan Elias
Bonin, Julien
Robert, Marc
Peñeñory, Alicia Beatriz
author_role author
author2 Hajj, Viviane
Andrada, Diego Marcelo
Argüello, Juan Elias
Bonin, Julien
Robert, Marc
Peñeñory, Alicia Beatriz
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Photochemistry
Carbonyl Groups
Radical Cation
Dithiane
topic Photochemistry
Carbonyl Groups
Radical Cation
Dithiane
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Photodeprotection of 1,3-dithianes in the presence of thiapyrylium was performed to return to the parent carbonyl compound, and the mechanism was studied by steady state photolysis, laser flash photolysis, and theoretical calculations. Electron transfer from dithianes to triplet sensitizers is extremely fast, and the decay of dithiane radical cations was not affected by the presence of water or oxygen as the consequence of a favorable unimolecular fragmentation pathway. Similar behaviors were observed for dithianes bearing electron-releasing or electron-withdrawing substituents on the aryl moiety, evidenced by C−S bond cleavage to form a distonic radical cation species. The lack of reaction under nitrogen atmosphere, requirement of oxygen for good conversion yields, inhibition of the photodeprotection process by the presence of pbenzoquinone, and absence of a labeled carbonyl final product when the reaction is performed in the presence of H2 18O all suggest that the superoxide anion drives the deprotection reaction. Density functional theory computational studies on the reactions with water, molecular oxygen, and the superoxide radical anion support the experimental findings.
Fil: Oksdath Mansilla, Gabriela. 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: Hajj, Viviane. Université Paris Diderot - Paris 7; Francia
Fil: Andrada, Diego Marcelo. Philipps-Universität Marburg; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Argüello, Juan Elias. 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: Bonin, Julien. Université Paris Diderot - Paris 7; Francia
Fil: Robert, Marc. Université Paris Diderot - Paris 7; Francia
Fil: Peñeñory, Alicia 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 Photodeprotection of 1,3-dithianes in the presence of thiapyrylium was performed to return to the parent carbonyl compound, and the mechanism was studied by steady state photolysis, laser flash photolysis, and theoretical calculations. Electron transfer from dithianes to triplet sensitizers is extremely fast, and the decay of dithiane radical cations was not affected by the presence of water or oxygen as the consequence of a favorable unimolecular fragmentation pathway. Similar behaviors were observed for dithianes bearing electron-releasing or electron-withdrawing substituents on the aryl moiety, evidenced by C−S bond cleavage to form a distonic radical cation species. The lack of reaction under nitrogen atmosphere, requirement of oxygen for good conversion yields, inhibition of the photodeprotection process by the presence of pbenzoquinone, and absence of a labeled carbonyl final product when the reaction is performed in the presence of H2 18O all suggest that the superoxide anion drives the deprotection reaction. Density functional theory computational studies on the reactions with water, molecular oxygen, and the superoxide radical anion support the experimental findings.
publishDate 2015
dc.date.none.fl_str_mv 2015-02
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/11336/43437
Oksdath Mansilla, Gabriela; Hajj, Viviane; Andrada, Diego Marcelo; Argüello, Juan Elias; Bonin, Julien; et al.; Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group; American Chemical Society; Journal of Organic Chemistry; 80; 5; 2-2015; 2733-2739
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/43437
identifier_str_mv Oksdath Mansilla, Gabriela; Hajj, Viviane; Andrada, Diego Marcelo; Argüello, Juan Elias; Bonin, Julien; et al.; Photoremoval of Protecting Groups: Mechanistic Aspects of 1,3- Dithiane Conversion to a Carbonyl Group; American Chemical Society; Journal of Organic Chemistry; 80; 5; 2-2015; 2733-2739
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jo502953t
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo502953t
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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