000048366 001__ 48366
000048366 005__ 20200221144325.0
000048366 0247_ $$2doi$$a10.1039/c6ra02638a
000048366 0248_ $$2sideral$$a94091
000048366 037__ $$aART-2016-94091
000048366 041__ $$aeng
000048366 100__ $$0(orcid)0000-0002-5288-9345$$aRoca-López, D.
000048366 245__ $$aRevisiting oxime-nitrone tautomerism. Evidence of nitrone tautomer participation in oxime nucleophilic addition reactions
000048366 260__ $$c2016
000048366 5060_ $$aAccess copy available to the general public$$fUnrestricted
000048366 5203_ $$aThe oxime-nitrone tautomerism has been revisited using high-level DFT calculations. The isomerization has been found to be more favorable through a bimolecular process involving two molecules of oxime, a finding that argues against the commonly accepted thermal 1,2-H-shift mechanism. The reaction of arylamidoximes with 1,2-diaza-1,3-dienes to yield the corresponding O-substituted oximes (stable intermediates for the synthesis of 1,2,4-oxadiazine derivatives) was also investigated as a rare case in which O-alkylation is observed in the reaction between oximes and electron-poor alkenes in the absence of a base. Under such conditions the reaction usually proceeds through the nucleophilic attack of the oxime nitrogen to yield the corresponding nitrone. The computational investigation revealed that in the case of arylamidoximes, the pathway involving the less stable but more reactive nitrone tautomer is the predominant mechanism, evidencing for the first time the involvement of a nitrone tautomer in nucleophilic additions of oximes. Validation of the model has been carried out by studying alternative ene-like processes; the dramatically different reactivity predicted for arylamidoximes and unsubstituted oxime are rationalized in terms of steric hindrance.
000048366 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E10$$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2013-44367-C2-1-P
000048366 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000048366 590__ $$a3.108$$b2016
000048366 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b59 / 166 = 0.355$$c2016$$dQ2$$eT2
000048366 592__ $$a0.889$$b2016
000048366 593__ $$aChemistry (miscellaneous)$$c2016$$dQ1
000048366 593__ $$aChemical Engineering (miscellaneous)$$c2016$$dQ1
000048366 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000048366 700__ $$aDarù, A.
000048366 700__ $$0(orcid)0000-0003-3433-6701$$aTejero, T.$$uUniversidad de Zaragoza
000048366 700__ $$0(orcid)0000-0002-2202-3460$$aMerino, P.$$uUniversidad de Zaragoza
000048366 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000048366 773__ $$g6, 26 (2016), 22161-22173$$pRSC ADVANCES$$tRSC Advances$$x2046-2069
000048366 8564_ $$s1334457$$uhttps://zaguan.unizar.es/record/48366/files/texto_completo.pdf$$yVersión publicada
000048366 8564_ $$s112242$$uhttps://zaguan.unizar.es/record/48366/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000048366 909CO $$ooai:zaguan.unizar.es:48366$$particulos$$pdriver
000048366 951__ $$a2020-02-21-13:43:17
000048366 980__ $$aARTICLE