000060992 001__ 60992 000060992 005__ 20190709135532.0 000060992 0247_ $$2doi$$a10.1039/c7sc00009j 000060992 0248_ $$2sideral$$a98569 000060992 037__ $$aART-2017-98569 000060992 041__ $$aeng 000060992 100__ $$aOrue, A. 000060992 245__ $$aRacemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1, 4-addition/Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights 000060992 260__ $$c2017 000060992 5060_ $$aAccess copy available to the general public$$fUnrestricted 000060992 5203_ $$a2-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. 000060992 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E10$$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2013-44367-C2-1-P$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52107-P$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R 000060992 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttp://creativecommons.org/licenses/by-nc/3.0/es/ 000060992 590__ $$a9.063$$b2017 000060992 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b18 / 171 = 0.105$$c2017$$dQ1$$eT1 000060992 592__ $$a4.508$$b2017 000060992 593__ $$aChemistry (miscellaneous)$$c2017$$dQ1 000060992 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000060992 700__ $$aUria, U. 000060992 700__ $$0(orcid)0000-0002-5288-9345$$aRoca-López, D. 000060992 700__ $$0(orcid)0000-0001-8355-2289$$aDelso, I.$$uUniversidad de Zaragoza 000060992 700__ $$aReyes, E. 000060992 700__ $$aCarrillo, L. 000060992 700__ $$0(orcid)0000-0002-2202-3460$$aMerino, P.$$uUniversidad de Zaragoza 000060992 700__ $$aVicario, J. L. 000060992 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica 000060992 773__ $$g8, 4 (2017), 2904-2913$$pChem. sci.$$tCHEMICAL SCIENCE$$x2041-6520 000060992 8564_ $$s839687$$uhttps://zaguan.unizar.es/record/60992/files/texto_completo.pdf$$yVersión publicada 000060992 8564_ $$s116408$$uhttps://zaguan.unizar.es/record/60992/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000060992 909CO $$ooai:zaguan.unizar.es:60992$$particulos$$pdriver 000060992 951__ $$a2019-07-09-12:02:59 000060992 980__ $$aARTICLE