dc.contributor.author | Orue Dañobeitia, Ane | |
dc.contributor.author | Uria Pujana, Uxue | |
dc.contributor.author | Roca-López, David | |
dc.contributor.author | Delso, Ignacio | |
dc.contributor.author | Reyes Martín, Efraim | |
dc.contributor.author | Carrillo Fernández, María Luisa | |
dc.contributor.author | Merino, Pedro | |
dc.contributor.author | Vicario Hernando, José Luis | |
dc.date.accessioned | 2018-06-18T08:21:22Z | |
dc.date.available | 2018-06-18T08:21:22Z | |
dc.date.issued | 2017-04-01 | |
dc.identifier.citation | chemical Science 8(4) : 2904-2913 (2017) | es_ES |
dc.identifier.issn | 2041-6520 | |
dc.identifier.issn | 2041-6539 | |
dc.identifier.uri | http://hdl.handle.net/10810/27571 | |
dc.description.abstract | 2-Hydroxydihydropyran-5-ones behave as excellent polyfunctional reagents able to react with enals through oxa-Michael/Michael process cascade under the combination of iminium and enamine catalysis. These racemic hemiacetalic compounds are used as unconventional O-pronucleophiles in the initial oxa-Michael reaction, also leading to the formation of a single stereoisomer under a dynamic kinetic resolution (DKR) process. Importantly, by using beta-aryl or beta-alkyl substituted alpha,beta-unsaturated substrates as initial Michael acceptors either kinetically or thermodynamically controlled diastereoisomers were formed with high stereoselection through the careful selection of the reaction conditions. Finally, a complete experimental and computational study confirmed the initially proposed DKR process during the catalytic oxa-Michael/Michael cascade reaction and also explained the kinetic/thermodynamic pathway operating in each case. | es_ES |
dc.description.sponsorship | This research was supported by the Spanish MINECO (FEDER-CTQ2014-52107-P, FEDER-CTQ2013-44367-C2-1-P and FEDER-CTQ2016-76155-R), the Basque Government (Grupos IT908-16), UPV/EHU (UFI QOSYC 11/22) and Government of Aragon (Grupos Consolidados, E.10). D. R.-L. thanks MEC for a predoctoral FPU fellowship. The authors thankfully acknowledge the resources from the supercomputers "Memento" and "Cierzo", technical expertise and assistance provided by BIFI-ZCAM (Universidad de Zaragoza, Spain). | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Royal Society of Chemistry | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/FEDER-CTQ2014-52107-P | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/FEDER-CTQ2013-44367-C2-1-P | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/FEDER-CTQ2016-76155-R | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by-nc/3.0/es/ | * |
dc.subject | oxa-michael reaction | es_ES |
dc.subject | enantioselective total-synthesis | es_ES |
dc.subject | c-heteroatom bonds | es_ES |
dc.subject | alpha,beta-unsaturated aldehydes | es_ES |
dc.subject | asymmetric-synthesis | es_ES |
dc.subject | conjugate addition | es_ES |
dc.subject | domino reactions | es_ES |
dc.subject | diastereoselective synthesis | es_ES |
dc.subject | carbonyl-compounds | es_ES |
dc.subject | organocatalytic epoxidation | es_ES |
dc.title | Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1,4-addition/ Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. | es_ES |
dc.rights.holder | Atribución-NoComercial 3.0 España | * |
dc.relation.publisherversion | http://pubs.rsc.org/en/content/articlelanding/2017/sc/c7sc00009j#!divAbstract | es_ES |
dc.identifier.doi | 10.1039/c7sc00009j | |
dc.departamentoes | Química orgánica II | es_ES |
dc.departamentoeu | Kimika organikoa II | es_ES |