Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers

The tandem gold(I)-catalyzed propargyl Claisen rearrangement/hydroarylation reaction of suitable propargyl vinyl ethers, followed by in situ reduction of the resulting carbonyl group, provides functionalized indenes in good to excellent yields. The reaction occurs at room temperature in dichlorometh...

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Autores: Rinaldi, Antonia, Langé, Vittoria, Gómez Bengoa, Enrique, Zanella, Giovanna, Scarpi, Dina, Occhiato, Ernesto G
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/52144
Acceso en línea:http://hdl.handle.net/10810/52144
Access Level:acceso abierto
Palabra clave:ligands
allenes
cyclization
vinyl
propargyls
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spelling Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl EthersRinaldi, AntoniaLangé, VittoriaGómez Bengoa, EnriqueZanella, GiovannaScarpi, DinaOcchiato, Ernesto GligandsallenescyclizationvinylpropargylsThe tandem gold(I)-catalyzed propargyl Claisen rearrangement/hydroarylation reaction of suitable propargyl vinyl ethers, followed by in situ reduction of the resulting carbonyl group, provides functionalized indenes in good to excellent yields. The reaction occurs at room temperature in dichloromethane in the presence of 3 mol % [IPrAuCl]/AgBF4 as the best catalytic system. With phosphine ligands no cyclization of the allene intermediate instead occurs. A variety of substituents and functional groups present on the substrate are tolerated. The effect of the aryl ring substituents and the results of a DFT computational study suggest that the final hydroarylation is the rate determining step of this cascade process. Further in situ chain elongation, prior final work up of the tandem process, can be carried out by Wittig olefination of the aldehyde functionality, thus incrementing the diversity of the products obtainedFinancial support from University of Florence is acknowledged. Dr Alessandro Pratesi and Dr Susanna Pucci are acknowledged for technical assistance. Ente Cassa di Risparmio di Firenze is acknowledged for granting a 400 MHz NMR instrument. G.Z. and E.G.-B. thank the European Funding Horizon 2020-MSCA (ITN-EJD CATMEC 14/06-721223) and also SGiker (UPV/EHU) for human and technical support.ACSEuropean Commission202120212019info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/52144reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/EC/H2020/721223https://pubs.acs.org/doi/10.1021/acs.joc.9b00646info:eu-repo/semantics/openAccess© 2019 American Chemical Societyoai:addi.ehu.eus:10810/521442026-06-18T09:23:17Z
dc.title.none.fl_str_mv Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
title Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
spellingShingle Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
Rinaldi, Antonia
ligands
allenes
cyclization
vinyl
propargyls
title_short Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
title_full Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
title_fullStr Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
title_full_unstemmed Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
title_sort Synthesis of Indenes by the Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers
dc.creator.none.fl_str_mv Rinaldi, Antonia
Langé, Vittoria
Gómez Bengoa, Enrique
Zanella, Giovanna
Scarpi, Dina
Occhiato, Ernesto G
author Rinaldi, Antonia
author_facet Rinaldi, Antonia
Langé, Vittoria
Gómez Bengoa, Enrique
Zanella, Giovanna
Scarpi, Dina
Occhiato, Ernesto G
author_role author
author2 Langé, Vittoria
Gómez Bengoa, Enrique
Zanella, Giovanna
Scarpi, Dina
Occhiato, Ernesto G
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
dc.subject.none.fl_str_mv ligands
allenes
cyclization
vinyl
propargyls
topic ligands
allenes
cyclization
vinyl
propargyls
description The tandem gold(I)-catalyzed propargyl Claisen rearrangement/hydroarylation reaction of suitable propargyl vinyl ethers, followed by in situ reduction of the resulting carbonyl group, provides functionalized indenes in good to excellent yields. The reaction occurs at room temperature in dichloromethane in the presence of 3 mol % [IPrAuCl]/AgBF4 as the best catalytic system. With phosphine ligands no cyclization of the allene intermediate instead occurs. A variety of substituents and functional groups present on the substrate are tolerated. The effect of the aryl ring substituents and the results of a DFT computational study suggest that the final hydroarylation is the rate determining step of this cascade process. Further in situ chain elongation, prior final work up of the tandem process, can be carried out by Wittig olefination of the aldehyde functionality, thus incrementing the diversity of the products obtained
publishDate 2019
dc.date.none.fl_str_mv 2019
2021
2021
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/52144
url http://hdl.handle.net/10810/52144
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/H2020/721223
https://pubs.acs.org/doi/10.1021/acs.joc.9b00646
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
© 2019 American Chemical Society
eu_rights_str_mv openAccess
rights_invalid_str_mv © 2019 American Chemical Society
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869414705203773440
score 15,300724

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