TY - JOUR
T1 - Acyl Group Migration in Pyranosides as Studied by Experimental and Computational Methods
AU - Lassfolk, Robert
AU - Pedrón, Manuel
AU - Tejero, Tomás
AU - Merino, Pedro
AU - Wärnå, Johan
AU - Leino, Reko
N1 - Funding Information:
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.). The authors thankfully acknowledge the resources from the supercomputers “Memento” and “Cierzo”, technical expertise and assistance provided by BIFI‐ZCAM (Universidad de Zaragoza, Spain).
Publisher Copyright:
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
PY - 2022/3/18
Y1 - 2022/3/18
N2 - 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.
AB - 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.
KW - acyl group migration
KW - carbohydrates
KW - computational chemistry
KW - NMR spectroscopy
KW - reaction mechanism
UR - http://www.scopus.com/inward/record.url?scp=85129715157&partnerID=8YFLogxK
U2 - 10.1002/chem.202200499
DO - 10.1002/chem.202200499
M3 - Article
C2 - 35302249
AN - SCOPUS:85129715157
SN - 0947-6539
VL - 28
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 34
M1 - e202200499
ER -