dc.creator | Romero Arenas, Antonio | es |
dc.creator | Hornillos, Valentín | es |
dc.creator | Iglesias Sigüenza, Francisco Javier | es |
dc.creator | Fernández Fernández, Rosario Fátima | es |
dc.creator | López Serrano, Joaquín | es |
dc.creator | Ros, Abel | es |
dc.creator | Lassaletta, José M. | es |
dc.date.accessioned | 2022-12-12T17:22:25Z | |
dc.date.available | 2022-12-12T17:22:25Z | |
dc.date.issued | 2020 | |
dc.identifier.citation | Romero Arenas, A., Hornillos, V., Iglesias Sigüenza, F.J., Fernández Fernández, R.F., López Serrano, J., Ros, A. y Lassaletta, J.M. (2020). Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes. Journal of the American Chemical Society, 142 (5), 2628-2639. https://doi.org/10.1021/jacs.9b12858. | |
dc.identifier.issn | 0002-7863 | es |
dc.identifier.issn | 1520-5126 | es |
dc.identifier.uri | https://hdl.handle.net/11441/140355 | |
dc.description.abstract | 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. | es |
dc.description.sponsorship | Ministerio de Ciencia e Innovación CTQ2013-48164-C2-1-P, CTQ2013-48164-C2-2-P, CTQ2016-75193-P, RYC-2013-12585, RYC-2017-22294 | es |
dc.description.sponsorship | Junta de Andalucía 2012/FQM 10787 | es |
dc.format | application/pdf | es |
dc.format.extent | 12 p. | es |
dc.language.iso | eng | es |
dc.publisher | American Chemical Society | es |
dc.relation.ispartof | Journal of the American Chemical Society, 142 (5), 2628-2639. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/acceptedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química orgánica | es |
dc.relation.projectID | CTQ2013-48164-C2-1-P | es |
dc.relation.projectID | CTQ2013-48164-C2-2-P | es |
dc.relation.projectID | CTQ2016-75193-P | es |
dc.relation.projectID | RYC-2013-12585 | es |
dc.relation.projectID | RYC-2017-22294 | es |
dc.relation.projectID | 2012/FQM 10787 | es |
dc.relation.publisherversion | https://dx.doi.org/10.1021/jacs.9b12858 | es |
dc.identifier.doi | 10.1021/jacs.9b12858 | es |
dc.journaltitle | Journal of the American Chemical Society | es |
dc.publication.volumen | 142 | es |
dc.publication.issue | 5 | es |
dc.publication.initialPage | 2628 | es |
dc.publication.endPage | 2639 | es |
dc.contributor.funder | Ministerio de Ciencia e Innovación (MICIN). España | es |
dc.contributor.funder | Junta de Andalucía | es |