000118096 001__ 118096
000118096 005__ 20251107103406.0
000118096 0247_ $$2doi$$a10.1002/chem.202200499
000118096 0248_ $$2sideral$$a128861
000118096 037__ $$aART-2022-128861
000118096 041__ $$aeng
000118096 100__ $$aLassfolk, Robert
000118096 245__ $$aAcyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods
000118096 260__ $$c2022
000118096 5060_ $$aAccess copy available to the general public$$fUnrestricted
000118096 5203_ $$aAcyl group migration affects the synthesis, isolation, manipulation and purification of all acylated organic compounds containing free hydroxyl groups, in particular carbohydrates. While several isolated studies on the migration phenomenon in different buffers have been reported, comprehensive insights into the overall migration process in different monosaccharides under similar conditions have been lacking. Here, we have studied the acyl migration in different monosaccharides using five different acyl groups by a combination of experimental, kinetic and theoretical tools. The results show that the anomeric configuration in the monosaccharide has a major influence on the migration rate, together with the relative configurations of the other hydroxyl groups and the nature of the migrating acyl group. Full mechanistic model, based on computations, demonstrates that the acyl migration proceeds through an anionic stepwise mechanism with linear dependence on the OH-] and the pK(a) of the hydroxyl group toward which the acyl group is migrating.
000118096 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E34-20R$$9info:eu-repo/grantAgreement/ES/MICIU/PID2019-104090RB-100
000118096 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000118096 590__ $$a4.3$$b2022
000118096 592__ $$a1.229$$b2022
000118096 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b66 / 178 = 0.371$$c2022$$dQ2$$eT2
000118096 593__ $$aCatalysis$$c2022$$dQ1
000118096 593__ $$aOrganic Chemistry$$c2022$$dQ1
000118096 593__ $$aChemistry (miscellaneous)$$c2022$$dQ1
000118096 594__ $$a8.8$$b2022
000118096 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000118096 700__ $$0(orcid)0000-0003-4249-6748$$aPedrón, Manuel$$uUniversidad de Zaragoza
000118096 700__ $$0(orcid)0000-0003-3433-6701$$aTejero, Tomás$$uUniversidad de Zaragoza
000118096 700__ $$0(orcid)0000-0002-2202-3460$$aMerino, Pedro$$uUniversidad de Zaragoza
000118096 700__ $$aWarna, Johan
000118096 700__ $$aLeino, Reko
000118096 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000118096 773__ $$g28, 34 (2022), e202200499 [12 pp.]$$pChemistry (Weinh.)$$tChemistry - A European Journal$$x0947-6539
000118096 8564_ $$s5273489$$uhttps://zaguan.unizar.es/record/118096/files/texto_completo.pdf$$yVersión publicada
000118096 8564_ $$s2645027$$uhttps://zaguan.unizar.es/record/118096/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000118096 909CO $$ooai:zaguan.unizar.es:118096$$particulos$$pdriver
000118096 951__ $$a2025-11-07-10:32:10
000118096 980__ $$aARTICLE