Premium
Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods
Author(s) -
Lassfolk Robert,
Pedrón Manuel,
Tejero Tomás,
Merino Pedro,
Wärnå Johan,
Leino Reko
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200499
Subject(s) - monosaccharide , anomer , acyl group , chemistry , group (periodic table) , acylation , stereochemistry , organic chemistry , catalysis
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.