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

Robert Lassfolk, Manuel Pedrón, Tomás Tejero, Pedro Merino, Johan Wärnå, Reko Leino*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

7 Citations (Scopus)
40 Downloads (Pure)

Abstract

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.

Original languageEnglish
Article numbere202200499
JournalChemistry - A European Journal
Volume28
Issue number34
DOIs
Publication statusPublished - 18 Mar 2022
MoE publication typeA1 Journal article-refereed

Keywords

  • acyl group migration
  • carbohydrates
  • computational chemistry
  • NMR spectroscopy
  • reaction mechanism

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