000060705 001__ 60705
000060705 005__ 20190709135454.0
000060705 0247_ $$2doi$$a10.1039/c6ob02768g
000060705 0248_ $$2sideral$$a98217
000060705 037__ $$aART-2017-98217
000060705 041__ $$aeng
000060705 100__ $$aRíos-Gutiérrez, M.
000060705 245__ $$aA molecular electron density theory study of the 3 + 2] cycloaddition reaction of nitrones with ketenes
000060705 260__ $$c2017
000060705 5060_ $$aAccess copy available to the general public$$fUnrestricted
000060705 5203_ $$aThe 3 + 2] cycloaddition (32CA) reaction between nitrones and ketenes has been studied within the Molecular Electron Density Theory (MEDT) at the Density Functional Theory (DFT) MPWB1K/6-311G(d, p) computational level. Analysis of the conceptual DFT reactivity indices allows the explanation of the reactivity, and the chemo- and regioselectivity experimentally observed. The particular mechanism of this 32CA reaction involving low electrophilic ketenes has been elucidated by using a bonding evolution theory (BET) study. It is determined that this reaction takes place in one kinetic step only but in a non-concerted manner since two stages are clearly identified. Indeed, the formation of the second C-O bond begins when the first O-C bond is already formed. This study has also been applied to predict the reactivity of nitrones with highly electrophilic ketenes. Interestingly, this study predicts a switch to a two-step mechanism due to the higher polar character of this zw-type 32CA reaction. In both cases, BET supports the non-concerted nature of the 32CA reactions between nitrones and ketenes.
000060705 536__ $$9info:eu-repo/grantAgreement/ES/MINECO/BES-2014-068258$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-78669-P
000060705 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000060705 590__ $$a3.423$$b2017
000060705 591__ $$aCHEMISTRY, ORGANIC$$b16 / 57 = 0.281$$c2017$$dQ2$$eT1
000060705 592__ $$a1.281$$b2017
000060705 593__ $$aOrganic Chemistry$$c2017$$dQ1
000060705 593__ $$aPhysical and Theoretical Chemistry$$c2017$$dQ1
000060705 593__ $$aBiochemistry$$c2017$$dQ2
000060705 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000060705 700__ $$aDarù, A.
000060705 700__ $$0(orcid)0000-0003-3433-6701$$aTejero, T.$$uUniversidad de Zaragoza
000060705 700__ $$aDomingo, L.R.
000060705 700__ $$0(orcid)0000-0002-2202-3460$$aMerino, P.$$uUniversidad de Zaragoza
000060705 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000060705 773__ $$g15, 7 (2017), 1618-1627$$pOrg. biomol. chem.$$tORGANIC & BIOMOLECULAR CHEMISTRY$$x1477-0520
000060705 8564_ $$s1309505$$uhttps://zaguan.unizar.es/record/60705/files/texto_completo.pdf$$yVersión publicada
000060705 8564_ $$s101155$$uhttps://zaguan.unizar.es/record/60705/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000060705 909CO $$ooai:zaguan.unizar.es:60705$$particulos$$pdriver
000060705 951__ $$a2019-07-09-11:42:24
000060705 980__ $$aARTICLE