dc.creator | León García, Félix | es |
dc.creator | González-Liste, Pedro J. | es |
dc.creator | García-Garrido, Sergio E. | es |
dc.creator | Arribas Nieto, Inmaculada | es |
dc.creator | Rubio, Miguel | es |
dc.creator | Cadierno, Victorio | es |
dc.creator | Pizzano, Antonio | es |
dc.date.accessioned | 2018-05-24T17:12:27Z | |
dc.date.available | 2018-05-24T17:12:27Z | |
dc.date.issued | 2017 | |
dc.identifier.citation | León, F., González-Liste, P.J., García-Garrido, S.E., Arribas Nieto, I., Rubio, M., Cadierno, V. y Pizzano, A. (2017). Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters. Journal of Organic Chemistry, 82 (11), 5852-5867. | |
dc.identifier.issn | 1520-6904 | es |
dc.identifier.uri | https://hdl.handle.net/11441/75102 | |
dc.description.abstract | The catalytic asymmetric hydrogenation of trisubstituted enol esters using Rh catalysts bearing chiral phosphine-phosphite ligands (P-OP) has been studied. Substrates covered comprise α,β-dialkyl, α-alkyl-β-aryl, and α,β-diarylvinyl esters, the corresponding hydrogenation products being suitable precursors to prepare synthetically relevant chiral nonfunctionalized alcohols. A comparison of reactivity indicates that it decreases in the order: α,β-dialkyl > α-alkyl-β-aryl > α,β-diaryl. Based on the highly modular structure of P-OP ligands employed, catalyst screening identified highly enantioselective catalysts for α,β-dialkyl (95-99% ee) and nearly all of α-alkyl-β-aryl substrates (92-98% ee), with the exception of α-cyclohexyl-β-phenylvinyl acetate which exhibited a low enantioselectivity (47% ee). Finally, α,β-diarylvinyl substrates showed somewhat lower enantioselectivities (79-92% ee). In addition, some of the catalysts provided a high enantioselectivity in the hydrogenation of E/Z mixtures (ca. Z/E = 75:25) of α,β-dialkylvinyl substrates, while a dramatic decrease on enantioselectivity was observed in the case of α-methyl-β-anisylvinyl acetate (Z/E = 58:42). Complementary deuteration reactions are in accord with a highly enantioselective hydrogenation for both olefin isomers in the case of α,β-dialkylvinyl esters. In contrast, deuteration shows a complex behavior for α-methyl-β-anisylvinyl acetate derived from the participation of the E isomer in the reaction. | es |
dc.description.sponsorship | Ministerio de Economia, Industria y Competitividad of Spain CTQ2013-42501-P, CTQ2013-40591-P, CTQ2016-75193-P, CTQ2016-75986-P, CTQ2016-81797-REDC; AEI/FEDER | es |
dc.description.sponsorship | Gobierno de Asturias GRUPIN14-006 | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | American Chemical Society | es |
dc.relation.ispartof | Journal of Organic Chemistry, 82 (11), 5852-5867. | |
dc.rights | Atribución-NoComercial-SinDerivadas 3.0 Estados Unidos de América | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters | es |
dc.type | info:eu-repo/semantics/article | es |
dc.type.version | info:eu-repo/semantics/submittedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.relation.publisherversion | http://dx.doi.org/10.1021/acs.joc.7b00710 | es |
dc.identifier.doi | 10.1021/acs.joc.7b00710 | es |
idus.format.extent | 58 | es |
dc.journaltitle | Journal of Organic Chemistry | es |
dc.publication.volumen | 82 | es |
dc.publication.issue | 11 | es |
dc.publication.initialPage | 5852 | es |
dc.publication.endPage | 5867 | es |
dc.contributor.funder | Ministerio de Economia, Industria y Competitividad (MINECO). España | |
dc.contributor.funder | Principado de Asturias | |