Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles

[EN]: Versatile routes that lead to a variety of functionalized enantiopure tetrahydrofurans, dihydropyrans, and tetrahydrooxepines are based on chemo-, regio-, and stereocontrolled metal-catalyzed oxycyclization reactions of β,- and ,δ-allendiols, which were readily prepared from (R)-2,3-O-isopropy...

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Detalhes bibliográficos
Autores: Alcaide, Benito, Almendros, Pedro, Carrascosa, Rocío, Martínez del Campo, Teresa
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2010
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/29533
Acesso em linha:http://hdl.handle.net/10261/29533
Access Level:acceso abierto
Palavra-chave:Allenes
Cyclization
Gold
Palladium
Platinum
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spelling Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of OxacyclesAlcaide, BenitoAlmendros, PedroCarrascosa, RocíoMartínez del Campo, TeresaAllenesCyclizationGoldPalladiumPlatinum[EN]: Versatile routes that lead to a variety of functionalized enantiopure tetrahydrofurans, dihydropyrans, and tetrahydrooxepines are based on chemo-, regio-, and stereocontrolled metal-catalyzed oxycyclization reactions of β,- and ,δ-allendiols, which were readily prepared from (R)-2,3-O-isopropylideneglyceraldehyde. The application of PdII, PtII, AuIII, or LaIII salts as the catalysts gives controlled access to differently sized oxacycles in enantiopure form. Usually, chemoselective cyclization reactions occurred exclusively by attack of the secondary hydroxy group (except for the oxybromination of phenyl β,-allenic diols 3 b and 3 d) to an allenic carbon atom. Regio- and stereocontrol issues are mainly influenced by the nature of the metal catalysts and substituents.[ES]: Se han encontrado rutas versátiles que conducen a tetrahidrooxepinas, dihidropiranos y tetrahidrofuranos funcionalizados enantiopuros, basadas en reacciones de oxiciclación quimio-, regio- y estereocontroladas de β,- y ,δ-alenildioles catalizadas por metales. Los dioles de partida se prepararon fácilmente a partir de (R)-2,3-O-isopropilidengliceraldehido. La utilización de sales de PdII, PtII, AuIIIó LaIIIcomo catalizadores da lugar a un método de preparación controlada de oxaciclos de diferente tamaño en forma enantiopura. Normalmente, las reacciones de ciclación quimioselectiva ocurren exclusivamente por ataque del grupo hidroxilo secundario (excepto en la oxibromación de los fenil β,-alenildioles 3 b y 3 d) a uno de los carbonos alénicos. Tanto el control regio- como el estereoquímico están influídos por la naturaleza del metal y los sustituyentes.Support for this study by the DGI-MICINN (Project CTQ2009-09318), Comunidad Autónoma de Madrid and Fondo Social Europeo-EU (Project S2009/PPQ-1752), and UCM-BSCH (Project GR58/08) are gratefully acknowledged. T.M.C. and R.C. thank the MEC for predoctoral grants.Peer reviewedWiley-BlackwellComunidad de MadridMinisterio de Educación y Ciencia (España)Banco SantanderUniversidad Complutense de MadridEuropean CommissionMinisterio de Ciencia e Innovación (España)201020102010info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/29533reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE#S2009/PPQ-1752/CAPOTEhttp://dx.doi.org/10.1002/chem.201001520info:eu-repo/semantics/openAccessoai:digital.csic.es:10261/295332026-05-22T06:33:51Z
dc.title.none.fl_str_mv Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
title Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
spellingShingle Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
Alcaide, Benito
Allenes
Cyclization
Gold
Palladium
Platinum
title_short Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
title_full Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
title_fullStr Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
title_full_unstemmed Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
title_sort Metal-Catalyzed Cycloetherification Reactions of β,y- and y,δ-Allendiols: Chemo-, Regio-, and Stereocontrol in the Synthesis of Oxacycles
dc.creator.none.fl_str_mv Alcaide, Benito
Almendros, Pedro
Carrascosa, Rocío
Martínez del Campo, Teresa
author Alcaide, Benito
author_facet Alcaide, Benito
Almendros, Pedro
Carrascosa, Rocío
Martínez del Campo, Teresa
author_role author
author2 Almendros, Pedro
Carrascosa, Rocío
Martínez del Campo, Teresa
author2_role author
author
author
dc.contributor.none.fl_str_mv Comunidad de Madrid
Ministerio de Educación y Ciencia (España)
Banco Santander
Universidad Complutense de Madrid
European Commission
Ministerio de Ciencia e Innovación (España)
dc.subject.none.fl_str_mv Allenes
Cyclization
Gold
Palladium
Platinum
topic Allenes
Cyclization
Gold
Palladium
Platinum
description [EN]: Versatile routes that lead to a variety of functionalized enantiopure tetrahydrofurans, dihydropyrans, and tetrahydrooxepines are based on chemo-, regio-, and stereocontrolled metal-catalyzed oxycyclization reactions of β,- and ,δ-allendiols, which were readily prepared from (R)-2,3-O-isopropylideneglyceraldehyde. The application of PdII, PtII, AuIII, or LaIII salts as the catalysts gives controlled access to differently sized oxacycles in enantiopure form. Usually, chemoselective cyclization reactions occurred exclusively by attack of the secondary hydroxy group (except for the oxybromination of phenyl β,-allenic diols 3 b and 3 d) to an allenic carbon atom. Regio- and stereocontrol issues are mainly influenced by the nature of the metal catalysts and substituents.
publishDate 2010
dc.date.none.fl_str_mv 2010
2010
2010
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/10261/29533
url http://hdl.handle.net/10261/29533
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
S2009/PPQ-1752/CAPOTE
http://dx.doi.org/10.1002/chem.201001520
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-Blackwell
publisher.none.fl_str_mv Wiley-Blackwell
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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