118096 20251107103406.0 doi 10.1002/chem.202200499 sideral 128861 ART-2022-128861 eng Lassfolk, Robert Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods 2022 Access copy available to the general public Unrestricted Acyl 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. info:eu-repo/grantAgreement/ES/DGA/E34-20R info:eu-repo/grantAgreement/ES/MICIU/PID2019-104090RB-100 info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es 4.3 2022 CHEMISTRY, MULTIDISCIPLINARY 66 / 178 = 0.371 2022 Q2 T2 1.229 2022 Catalysis 2022 Q1 Organic Chemistry 2022 Q1 Chemistry (miscellaneous) 2022 Q1 8.8 2022 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Pedrón, Manuel Universidad de Zaragoza (orcid)0000-0003-4249-6748 Tejero, Tomás Universidad de Zaragoza (orcid)0000-0003-3433-6701 Merino, Pedro Universidad de Zaragoza (orcid)0000-0002-2202-3460 Warna, Johan Leino, Reko 2013 765 Universidad de Zaragoza Dpto. Química Orgánica Área Química Orgánica 28, 34 (2022), e202200499 [12 pp.] Chemistry (Weinh.) Chemistry - A European Journal 0947-6539 5273489 http://zaguan.unizar.es/record/118096/files/texto_completo.pdf Versión publicada 2645027 http://zaguan.unizar.es/record/118096/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:118096 articulos driver 2025-11-07-10:32:10 ARTICLE