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

Autor: Robert Lassfolk, Manuel Pedrón, Tomás Tejero, Pedro Merino, Johan Wärnå, Reko Leino
Přispěvatelé: Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Gobierno de Aragón, Magnus Ehrnrooth Foundation
Rok vydání: 2022
Předmět:
Zdroj: Zaguán. Repositorio Digital de la Universidad de Zaragoza
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ISSN: 1521-3765
Popis: 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 pKa of the hydroxyl group toward which the acyl group is migrating.
Robert Lassfolk thanks the Magnus Ehrnrooth foundation and the Waldemar von Frenckell foundation for financial support. This research was also supported by the Spanish MICIU (PID2019-104090RB-100) and Government of Aragón (Grupos Consolidados, E34_20R and a fellowship to M. P.).
Databáze: OpenAIRE
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