Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group

A series of four α‐diketones placed as 1α‐pyruvoyl tethers on D‐glucopyranose and D‐glucopyranosiduronic acid skeletons was prepared in order to determine the influence of captodative and stereoelectronic effects on the regioselectivity of the hydrogen atom transfer (HAT) in Norrish type II photoche...

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Detalles Bibliográficos
Autores: Álvarez-Dorta, Dimitri, León, Elisa I., Kennedy, Alan R., Martín, Ángeles, Pérez-Martín, Inés, Riesco-Fagundo, Concepción, Suárez, Ernesto
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2014
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/179894
Acceso en línea:http://hdl.handle.net/10261/179894
Access Level:acceso abierto
Palabra clave:Photochemistry
Radicals
Diketones
Carbohydrates
Cyclization
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spelling Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl groupÁlvarez-Dorta, DimitriLeón, Elisa I.Kennedy, Alan R.Martín, ÁngelesPérez-Martín, InésRiesco-Fagundo, ConcepciónSuárez, ErnestoPhotochemistryRadicalsDiketonesCarbohydratesCyclizationA series of four α‐diketones placed as 1α‐pyruvoyl tethers on D‐glucopyranose and D‐glucopyranosiduronic acid skeletons was prepared in order to determine the influence of captodative and stereoelectronic effects on the regioselectivity of the hydrogen atom transfer (HAT) in Norrish type II photochemical processes. We observed that the 1,5‐HAT regioselectivity can be switched between the two potentially abstractable syn‐1,3‐diaxial hydrogens at H6 and H8. Highly unusual photoproducts from Norrish type II photoelimination and Norrish–Yang photocyclization initiated by the excited internal carbonyl group were obtained, in some cases in excellent synthetic yield. The 1,5‐HAT transition state in the Norrish type II photoelimination was investigated by photochemical experiments in the crystalline state.This work was supported by the Investigation Programs of the Ministerio de Economía y Competitividad (CTQ2010‐18244) and of the Gobierno de Canarias (SolSub20081000192). D.A.‐D. thanks the Ministerio de Economía y Competitividad for a fellowship. C.R.‐F. thanks the Programa I3P‐CSIC for a postdoctoral contract.Peer ReviewedWiley-VCHGobierno de CanariasMinisterio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2019201920142019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/179894reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttps://doi.org/10.1002/chem.201303843Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1798942026-05-22T06:33:51Z
dc.title.none.fl_str_mv Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
title Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
spellingShingle Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
Álvarez-Dorta, Dimitri
Photochemistry
Radicals
Diketones
Carbohydrates
Cyclization
title_short Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
title_full Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
title_fullStr Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
title_full_unstemmed Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
title_sort Photochemistry of α-diketones in carbohydrates: Anomalous norrish typea II photoelimination and norrish-yang photocyclization promoted by the internal carbonyl group
dc.creator.none.fl_str_mv Álvarez-Dorta, Dimitri
León, Elisa I.
Kennedy, Alan R.
Martín, Ángeles
Pérez-Martín, Inés
Riesco-Fagundo, Concepción
Suárez, Ernesto
author Álvarez-Dorta, Dimitri
author_facet Álvarez-Dorta, Dimitri
León, Elisa I.
Kennedy, Alan R.
Martín, Ángeles
Pérez-Martín, Inés
Riesco-Fagundo, Concepción
Suárez, Ernesto
author_role author
author2 León, Elisa I.
Kennedy, Alan R.
Martín, Ángeles
Pérez-Martín, Inés
Riesco-Fagundo, Concepción
Suárez, Ernesto
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Gobierno de Canarias
Ministerio de Economía y Competitividad (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Photochemistry
Radicals
Diketones
Carbohydrates
Cyclization
topic Photochemistry
Radicals
Diketones
Carbohydrates
Cyclization
description A series of four α‐diketones placed as 1α‐pyruvoyl tethers on D‐glucopyranose and D‐glucopyranosiduronic acid skeletons was prepared in order to determine the influence of captodative and stereoelectronic effects on the regioselectivity of the hydrogen atom transfer (HAT) in Norrish type II photochemical processes. We observed that the 1,5‐HAT regioselectivity can be switched between the two potentially abstractable syn‐1,3‐diaxial hydrogens at H6 and H8. Highly unusual photoproducts from Norrish type II photoelimination and Norrish–Yang photocyclization initiated by the excited internal carbonyl group were obtained, in some cases in excellent synthetic yield. The 1,5‐HAT transition state in the Norrish type II photoelimination was investigated by photochemical experiments in the crystalline state.
publishDate 2014
dc.date.none.fl_str_mv 2014
2019
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/179894
url http://hdl.handle.net/10261/179894
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1002/chem.201303843
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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