Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1, 4-addition/Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights
Orue, A. ; Uria, U. ; Roca-López, D. ; Delso, I. (Universidad de Zaragoza) ; Reyes, E. ; Carrillo, L. ; Merino, P. (Universidad de Zaragoza) ; Vicario, J. L.
Resumen: 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 ß-aryl or ß-alkyl substituted a, ß-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.
Idioma: Inglés
DOI: 10.1039/c7sc00009j
Año: 2017
Publicado en: CHEMICAL SCIENCE 8, 4 (2017), 2904-2913
ISSN: 2041-6520
Factor impacto JCR: 9.063 (2017)
Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 18 / 171 = 0.105 (2017) - Q1 - T1
Factor impacto SCIMAGO: 4.508 - Chemistry (miscellaneous) (Q1)
Financiación: info:eu-repo/grantAgreement/ES/DGA/E10
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2013-44367-C2-1-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52107-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes.
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Idioma: Inglés
DOI: 10.1039/c7sc00009j
Año: 2017
Publicado en: CHEMICAL SCIENCE 8, 4 (2017), 2904-2913
ISSN: 2041-6520
Factor impacto JCR: 9.063 (2017)
Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 18 / 171 = 0.105 (2017) - Q1 - T1
Factor impacto SCIMAGO: 4.508 - Chemistry (miscellaneous) (Q1)
Financiación: info:eu-repo/grantAgreement/ES/DGA/E10
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2013-44367-C2-1-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52107-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R
Tipo y forma: Article (Published version)
Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. Exportado de SIDERAL (2019-07-09-12:02:59)
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Record created 2017-05-03, last modified 2019-07-09