Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives

The excitation of the innermost carbonyl of nono‐2,3‐diulose derivatives by irradiation with visible‐light initiates a sequential Norrish type II photoelimination and aldol cyclization process that finally gives polyfunctionalized cyclopentitols. The rearrangement has been confirmed by the isolation...

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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:2013
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/178823
Acceso en línea:http://hdl.handle.net/10261/178823
Access Level:acceso abierto
Palabra clave:Cyclopentitols
Diketones
Photochemistry
Ring Contraction
Carbohydrates
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spelling Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivativesÁlvarez‐Dorta, DimitriLeón, Elisa I.Kennedy, Alan R.Martín, ÁngelesPérez-Martín, InésRiesco-Fagundo, ConcepciónSuárez, ErnestoCyclopentitolsDiketonesPhotochemistryRing ContractionCarbohydratesThe excitation of the innermost carbonyl of nono‐2,3‐diulose derivatives by irradiation with visible‐light initiates a sequential Norrish type II photoelimination and aldol cyclization process that finally gives polyfunctionalized cyclopentitols. The rearrangement has been confirmed by the isolation of stable acyclic photoenol intermediates that can be independently cyclized by a thermal 5‐(enolexo)‐exo‐trig uncatalyzed aldol reaction with high diastereoselectivity. In this last step, the large deuterium kinetic isotope effect found for the 1,5‐hydrogen atom transfer seems to indicate that the aldol reaction runs through a concerted pericyclic mechanism. Owing to the ready availability of pyranose sugars of various configurations, this protocol has been used to study the influence of pyranose ring‐substituents on the diastereoselectivity of the aldol cyclization reaction. In contrast with other pyranose ring contraction methodologies no transition‐metal reagents are needed and the sequential rearrangement occurs simply by using visible light and moderate heating (0 to 60 °C).This work was supported by the Investigation Programs (CTQ2010‐18244) of the Ministerio de Economía y Competitividad and (SolSub20081000192) of the Gobierno de Canarias. 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.Wiley-VCHGobierno de CanariasMinisterio de Economía y Competitividad (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2019201920132019info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/178823reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttps://doi.org/10.1002/chem.201301230Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1788232026-05-22T06:33:51Z
dc.title.none.fl_str_mv Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
title Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
spellingShingle Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
Álvarez‐Dorta, Dimitri
Cyclopentitols
Diketones
Photochemistry
Ring Contraction
Carbohydrates
title_short Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
title_full Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
title_fullStr Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
title_full_unstemmed Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
title_sort Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
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 Cyclopentitols
Diketones
Photochemistry
Ring Contraction
Carbohydrates
topic Cyclopentitols
Diketones
Photochemistry
Ring Contraction
Carbohydrates
description The excitation of the innermost carbonyl of nono‐2,3‐diulose derivatives by irradiation with visible‐light initiates a sequential Norrish type II photoelimination and aldol cyclization process that finally gives polyfunctionalized cyclopentitols. The rearrangement has been confirmed by the isolation of stable acyclic photoenol intermediates that can be independently cyclized by a thermal 5‐(enolexo)‐exo‐trig uncatalyzed aldol reaction with high diastereoselectivity. In this last step, the large deuterium kinetic isotope effect found for the 1,5‐hydrogen atom transfer seems to indicate that the aldol reaction runs through a concerted pericyclic mechanism. Owing to the ready availability of pyranose sugars of various configurations, this protocol has been used to study the influence of pyranose ring‐substituents on the diastereoselectivity of the aldol cyclization reaction. In contrast with other pyranose ring contraction methodologies no transition‐metal reagents are needed and the sequential rearrangement occurs simply by using visible light and moderate heating (0 to 60 °C).
publishDate 2013
dc.date.none.fl_str_mv 2013
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/10261/178823
url http://hdl.handle.net/10261/178823
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv https://doi.org/10.1002/chem.201301230
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 15,811543

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