Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings

Autores
Riveira, Martín Jorge; Trigo Mouriño, Pablo; Troche Pesqueira, Eduardo; Martin, Gary E.; Navarro Vázquez, Armando; Mischne, Mirta Paulina; Gil, Roberto R.
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The UVA (350 nm) irradiation of an α-pyran in the presence of oxygen led to the unexpected formation of a tetraoxygenated compound whose structure could not be unambiguously determined on the basis of conventional 1H-13C correlated experiments. 1,1-ADEQUATE (adequate double quantum transfer experiment) and 1,n-ADEQUATE combined with computer-assisted structure elucidation software led to two structural possibilities involving the formation of either an epoxide or an oxetane. Residual dipolar couplings allowed not only the identification of the compound as a spiroepoxide but also the determination of its relative configuration. To account for its formation, we propose a bisepoxide intermediate that, as opposed to most α,β-epoxyketones under irradiation, undergoes O-Cβ cleavage probably due to the presence of an extra oxygen substituent in the β position. 1,2-Acyl migration would then proceed stereoselectively to the final product obtained as a single diastereomer.
Fil: Riveira, Martín Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Trigo Mouriño, Pablo. University of Carnegie Mellon; Estados Unidos
Fil: Troche Pesqueira, Eduardo. University of Carnegie Mellon; Estados Unidos. Universidad de Vigo; España
Fil: Martin, Gary E.. Merck Research Laboratories; Estados Unidos
Fil: Navarro Vázquez, Armando. Universidade Federal de Pernambuco; Brasil
Fil: Mischne, Mirta Paulina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Gil, Roberto R.. University of Carnegie Mellon; Estados Unidos
Materia
STRUCTURE ELUCIDATION
PHOTOOXYGENATION
2H-PYRANS
RDC
NMR
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:11336/100742
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/100742
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar CouplingsRiveira, Martín JorgeTrigo Mouriño, PabloTroche Pesqueira, EduardoMartin, Gary E.Navarro Vázquez, ArmandoMischne, Mirta PaulinaGil, Roberto R.STRUCTURE ELUCIDATIONPHOTOOXYGENATION2H-PYRANSRDCNMRhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The UVA (350 nm) irradiation of an α-pyran in the presence of oxygen led to the unexpected formation of a tetraoxygenated compound whose structure could not be unambiguously determined on the basis of conventional 1H-13C correlated experiments. 1,1-ADEQUATE (adequate double quantum transfer experiment) and 1,n-ADEQUATE combined with computer-assisted structure elucidation software led to two structural possibilities involving the formation of either an epoxide or an oxetane. Residual dipolar couplings allowed not only the identification of the compound as a spiroepoxide but also the determination of its relative configuration. To account for its formation, we propose a bisepoxide intermediate that, as opposed to most α,β-epoxyketones under irradiation, undergoes O-Cβ cleavage probably due to the presence of an extra oxygen substituent in the β position. 1,2-Acyl migration would then proceed stereoselectively to the final product obtained as a single diastereomer.Fil: Riveira, Martín Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Trigo Mouriño, Pablo. University of Carnegie Mellon; Estados UnidosFil: Troche Pesqueira, Eduardo. University of Carnegie Mellon; Estados Unidos. Universidad de Vigo; EspañaFil: Martin, Gary E.. Merck Research Laboratories; Estados UnidosFil: Navarro Vázquez, Armando. Universidade Federal de Pernambuco; BrasilFil: Mischne, Mirta Paulina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Gil, Roberto R.. University of Carnegie Mellon; Estados UnidosAmerican Chemical Society2015-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/100742Riveira, Martín Jorge; Trigo Mouriño, Pablo; Troche Pesqueira, Eduardo; Martin, Gary E.; Navarro Vázquez, Armando; et al.; Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings; American Chemical Society; Journal of Organic Chemistry; 80; 15; 8-2015; 7396-74020022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.5b00817info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.joc.5b00817info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:54:13Zoai:ri.conicet.gov.ar:11336/100742instacron: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 09:54:13.625CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
title Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
spellingShingle Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
Riveira, Martín Jorge
STRUCTURE ELUCIDATION
PHOTOOXYGENATION
2H-PYRANS
RDC
NMR
title_short Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
title_full Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
title_fullStr Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
title_full_unstemmed Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
title_sort Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings
dc.creator.none.fl_str_mv Riveira, Martín Jorge
Trigo Mouriño, Pablo
Troche Pesqueira, Eduardo
Martin, Gary E.
Navarro Vázquez, Armando
Mischne, Mirta Paulina
Gil, Roberto R.
author Riveira, Martín Jorge
author_facet Riveira, Martín Jorge
Trigo Mouriño, Pablo
Troche Pesqueira, Eduardo
Martin, Gary E.
Navarro Vázquez, Armando
Mischne, Mirta Paulina
Gil, Roberto R.
author_role author
author2 Trigo Mouriño, Pablo
Troche Pesqueira, Eduardo
Martin, Gary E.
Navarro Vázquez, Armando
Mischne, Mirta Paulina
Gil, Roberto R.
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv STRUCTURE ELUCIDATION
PHOTOOXYGENATION
2H-PYRANS
RDC
NMR
topic STRUCTURE ELUCIDATION
PHOTOOXYGENATION
2H-PYRANS
RDC
NMR
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 UVA (350 nm) irradiation of an α-pyran in the presence of oxygen led to the unexpected formation of a tetraoxygenated compound whose structure could not be unambiguously determined on the basis of conventional 1H-13C correlated experiments. 1,1-ADEQUATE (adequate double quantum transfer experiment) and 1,n-ADEQUATE combined with computer-assisted structure elucidation software led to two structural possibilities involving the formation of either an epoxide or an oxetane. Residual dipolar couplings allowed not only the identification of the compound as a spiroepoxide but also the determination of its relative configuration. To account for its formation, we propose a bisepoxide intermediate that, as opposed to most α,β-epoxyketones under irradiation, undergoes O-Cβ cleavage probably due to the presence of an extra oxygen substituent in the β position. 1,2-Acyl migration would then proceed stereoselectively to the final product obtained as a single diastereomer.
Fil: Riveira, Martín Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Trigo Mouriño, Pablo. University of Carnegie Mellon; Estados Unidos
Fil: Troche Pesqueira, Eduardo. University of Carnegie Mellon; Estados Unidos. Universidad de Vigo; España
Fil: Martin, Gary E.. Merck Research Laboratories; Estados Unidos
Fil: Navarro Vázquez, Armando. Universidade Federal de Pernambuco; Brasil
Fil: Mischne, Mirta Paulina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: Gil, Roberto R.. University of Carnegie Mellon; Estados Unidos
description The UVA (350 nm) irradiation of an α-pyran in the presence of oxygen led to the unexpected formation of a tetraoxygenated compound whose structure could not be unambiguously determined on the basis of conventional 1H-13C correlated experiments. 1,1-ADEQUATE (adequate double quantum transfer experiment) and 1,n-ADEQUATE combined with computer-assisted structure elucidation software led to two structural possibilities involving the formation of either an epoxide or an oxetane. Residual dipolar couplings allowed not only the identification of the compound as a spiroepoxide but also the determination of its relative configuration. To account for its formation, we propose a bisepoxide intermediate that, as opposed to most α,β-epoxyketones under irradiation, undergoes O-Cβ cleavage probably due to the presence of an extra oxygen substituent in the β position. 1,2-Acyl migration would then proceed stereoselectively to the final product obtained as a single diastereomer.
publishDate 2015
dc.date.none.fl_str_mv 2015-08
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/11336/100742
Riveira, Martín Jorge; Trigo Mouriño, Pablo; Troche Pesqueira, Eduardo; Martin, Gary E.; Navarro Vázquez, Armando; et al.; Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings; American Chemical Society; Journal of Organic Chemistry; 80; 15; 8-2015; 7396-7402
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/100742
identifier_str_mv Riveira, Martín Jorge; Trigo Mouriño, Pablo; Troche Pesqueira, Eduardo; Martin, Gary E.; Navarro Vázquez, Armando; et al.; Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings; American Chemical Society; Journal of Organic Chemistry; 80; 15; 8-2015; 7396-7402
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/acs.joc.5b00817
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.joc.5b00817
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
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
_version_ 1844613648048193536
score 13.070432

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