Acetyl Group Migration in Xylan and Glucan Model Compounds as Studied by Experimental and Computational Methods

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

Resumen: It was recently demonstrated by us that acetyl groups in oligosaccharides can migrate not only within one saccharide unit but also between two different saccharide units. Kinetics of this phenomenon were previously investigated in both mannan model compounds and a naturally occurring polysaccharide. In addition to mannans, there are also several other naturally acetylated polysaccharides, such as xyloglucans and xylans. Both xyloglucans and xylans are some of the most common acetylated polysaccharides in nature, displaying important roles in the plant cells. Considering the various biological roles of natural polysaccharides, it could be hypothesized that the intramolecular migration of acetyl groups might also be associated with regulation of the biological activity of polysaccharides in nature. Consequently, a better understanding of the overall migration phenomenon across the glycosidic bonds could help to understand the potential role of such migrations in the context of the biological activity of polysaccharides. Here, we present a detailed investigation on acetyl group migration in the synthesized xylan and glucan trisaccharide model compounds by a combination of experimental and computational methods, showing that the migration between the saccharide units proceeds from a secondary hydroxyl group of one saccharide unit toward a primary hydroxyl group of the other unit.

Idioma: Inglés

DOI: 10.1021/acs.joc.2c01956

Año: 2022

Publicado en: Journal of Organic Chemistry 87, 21 (2022), 14544-14554
ISSN: 0022-3263

Factor impacto JCR: 3.6 (2022)

Categ. JCR: CHEMISTRY, ORGANIC rank: 10 / 52 = 0.192 (2022) - Q1 - T1

Factor impacto CITESCORE: 6.8 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.892 - Organic Chemistry (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)