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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/43437
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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 Técnicas2025-09-03T09:58:58Zoai: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:34982025-09-03 09:58:58.572CONICET 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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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1842269553631952896 |
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13.13397 |