Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods

Lassfolk, Robert ; Pedrón, Manuel (Universidad de Zaragoza) ; Tejero, Tomás (Universidad de Zaragoza) ; Merino, Pedro (Universidad de Zaragoza) ; Warna, Johan ; Leino, Reko

Resumen: 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.

Idioma: Inglés

DOI: 10.1002/chem.202200499

Año: 2022

Publicado en: Chemistry - A European Journal 28, 34 (2022), e202200499 [12 pp.]
ISSN: 0947-6539

Factor impacto JCR: 4.3 (2022)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 66 / 178 = 0.371 (2022) - Q2 - T2

Factor impacto CITESCORE: 8.8 - Chemistry (Q1) - Chemical Engineering (Q1)

Factor impacto SCIMAGO: 1.229 - Catalysis (Q1) - Organic Chemistry (Q1) - Chemistry (miscellaneous) (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E34-20R
Financiación: info:eu-repo/grantAgreement/ES/MICIU/PID2019-104090RB-100

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)