Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes

A highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, and norbornenes with a variety of aryl isoquinoline, quinazoline, and pic...

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Autores: Romero Arenas, Antonio, Hornillos, Valentín, Iglesias Sigüenza, Francisco Javier, Fernández Fernández, Rosario Fátima, López Serrano, Joaquín, Ros, Abel, Lassaletta, José M.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:idus.us.es:11441/140355
Acceso en línea:https://hdl.handle.net/11441/140355
https://doi.org/10.1021/jacs.9b12858
Access Level:acceso abierto
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spelling Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and BicycloalkenesRomero Arenas, AntonioHornillos, ValentínIglesias Sigüenza, Francisco JavierFernández Fernández, Rosario FátimaLópez Serrano, JoaquínRos, AbelLassaletta, José M.A highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, and norbornenes with a variety of aryl isoquinoline, quinazoline, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching complete branched/linear or exo/endo ratios and excellent diastereo- and enantiomeric excesses when in situ formed [IrI/Tol-SDP] or [IrI/Tol-BINAP] complexes are used as the catalysts. Deuterium labeling experiments and a comprehensive computational study suggest that, despite fast double bond migratory insertion into Ir-H, the reaction proceeds through a modified Chalk-Harrod mechanism, starting with selectivity-determining insertion into Ir-CAryl. The regioselectivity is controlled by the electron-donating alkoxy group, whereas diastereo- and enantioselectivity have a complex origin, which depend on the relative orientation of the alkoxy group and the establishment of adequate π-πinteractions between the biaryl and the phosphine.Ministerio de Ciencia e Innovación CTQ2013-48164-C2-1-P, CTQ2013-48164-C2-2-P, CTQ2016-75193-P, RYC-2013-12585, RYC-2017-22294Junta de Andalucía 2012/FQM 10787American Chemical SocietyQuímica OrgánicaMinisterio de Ciencia e Innovación (MICIN). EspañaJunta de Andalucía2020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/140355https://doi.org/10.1021/jacs.9b12858reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésJournal of the American Chemical Society, 142 (5), 2628-2639.CTQ2013-48164-C2-1-PCTQ2013-48164-C2-2-PCTQ2016-75193-PRYC-2013-12585RYC-2017-222942012/FQM 10787https://dx.doi.org/10.1021/jacs.9b12858info:eu-repo/semantics/openAccessoai:idus.us.es:11441/1403552026-06-17T12:51:07Z
dc.title.none.fl_str_mv Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
title Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
spellingShingle Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
Romero Arenas, Antonio
title_short Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
title_full Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
title_fullStr Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
title_full_unstemmed Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
title_sort Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes
dc.creator.none.fl_str_mv Romero Arenas, Antonio
Hornillos, Valentín
Iglesias Sigüenza, Francisco Javier
Fernández Fernández, Rosario Fátima
López Serrano, Joaquín
Ros, Abel
Lassaletta, José M.
author Romero Arenas, Antonio
author_facet Romero Arenas, Antonio
Hornillos, Valentín
Iglesias Sigüenza, Francisco Javier
Fernández Fernández, Rosario Fátima
López Serrano, Joaquín
Ros, Abel
Lassaletta, José M.
author_role author
author2 Hornillos, Valentín
Iglesias Sigüenza, Francisco Javier
Fernández Fernández, Rosario Fátima
López Serrano, Joaquín
Ros, Abel
Lassaletta, José M.
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Química Orgánica
Ministerio de Ciencia e Innovación (MICIN). España
Junta de Andalucía
description A highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, and norbornenes with a variety of aryl isoquinoline, quinazoline, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching complete branched/linear or exo/endo ratios and excellent diastereo- and enantiomeric excesses when in situ formed [IrI/Tol-SDP] or [IrI/Tol-BINAP] complexes are used as the catalysts. Deuterium labeling experiments and a comprehensive computational study suggest that, despite fast double bond migratory insertion into Ir-H, the reaction proceeds through a modified Chalk-Harrod mechanism, starting with selectivity-determining insertion into Ir-CAryl. The regioselectivity is controlled by the electron-donating alkoxy group, whereas diastereo- and enantioselectivity have a complex origin, which depend on the relative orientation of the alkoxy group and the establishment of adequate π-πinteractions between the biaryl and the phosphine.
publishDate 2020
dc.date.none.fl_str_mv 2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/11441/140355
https://doi.org/10.1021/jacs.9b12858
url https://hdl.handle.net/11441/140355
https://doi.org/10.1021/jacs.9b12858
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Journal of the American Chemical Society, 142 (5), 2628-2639.
CTQ2013-48164-C2-1-P
CTQ2013-48164-C2-2-P
CTQ2016-75193-P
RYC-2013-12585
RYC-2017-22294
2012/FQM 10787
https://dx.doi.org/10.1021/jacs.9b12858
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
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:idUS. Depósito de Investigación de la Universidad de Sevilla
instname:Universidad de Sevilla (US)
instname_str Universidad de Sevilla (US)
reponame_str idUS. Depósito de Investigación de la Universidad de Sevilla
collection idUS. Depósito de Investigación de la Universidad de Sevilla
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301603

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