Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
29 05 2020
29 05 2020
Historique:
received:
31
12
2019
accepted:
22
04
2020
entrez:
31
5
2020
pubmed:
31
5
2020
medline:
25
8
2020
Statut:
epublish
Résumé
Controlling the chemical glycosylation reaction remains the major challenge in the synthesis of oligosaccharides. Though 1,2-trans glycosidic linkages can be installed using neighboring group participation, the construction of 1,2-cis linkages is difficult and has no general solution. Long-range participation (LRP) by distal acyl groups may steer the stereoselectivity, but contradictory results have been reported on the role and strength of this stereoelectronic effect. It has been exceedingly difficult to study the bridging dioxolenium ion intermediates because of their high reactivity and fleeting nature. Here we report an integrated approach, using infrared ion spectroscopy, DFT computations, and a systematic series of glycosylation reactions to probe these ions in detail. Our study reveals how distal acyl groups can play a decisive role in shaping the stereochemical outcome of a glycosylation reaction, and opens new avenues to exploit these species in the assembly of oligosaccharides and glycoconjugates to fuel biological research.
Identifiants
pubmed: 32471982
doi: 10.1038/s41467-020-16362-x
pii: 10.1038/s41467-020-16362-x
pmc: PMC7260182
doi:
Substances chimiques
Dioxoles
0
Oligosaccharides
0
Selenium Compounds
0
glycosyl dioxolenium
0
Glucose
IY9XDZ35W2
Mannose
PHA4727WTP
Galactose
X2RN3Q8DNE
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
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