2023
DOI: 10.1021/jacs.3c08709
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Detection and Characterization of Rapidly Equilibrating Glycosylation Reaction Intermediates Using Exchange NMR

Frank F. J. de Kleijne,
Floor ter Braak,
Dimitrios Piperoudis
et al.
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Cited by 9 publications
(14 citation statements)
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“…The conformational restriction enforced by the benzylidene ring, thus, prevents the benzylidene mannosyl 1,3dioxolenium ion to adopt the electronically most-favorable geometry (the 1 C 4 conformation), rendering the formation of the 3-O-benzoyl benzylidene mannosyl 1,3-dioxanium more difficult than the formation of its 4,6-dibenzyl counterpart, explaining the results we previously obtained in our CEST-NMR studies. 29,41 The identified lowest energy conformers of the dioxanium and oxocarbenium cations were subsequently used to compute reference IR-spectra to aid in interpretation of the experimentally obtained spectra. 26,42 Figure 1a,b shows the computed spectra (filled) and the experimental spectra (black line) to confirm the formation of the dioxanium ions, as indicated by a characteristic dioxanium −[C−O] + stretch (∼1550 cm −1 ) and the absence of the oxocarbenium [C1� O5] + (∼1565 cm −1 ) and benzoyl C�O (∼1775 cm −1 ) stretches.…”
Section: ■ Results and Discussionmentioning
confidence: 99%
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“…The conformational restriction enforced by the benzylidene ring, thus, prevents the benzylidene mannosyl 1,3dioxolenium ion to adopt the electronically most-favorable geometry (the 1 C 4 conformation), rendering the formation of the 3-O-benzoyl benzylidene mannosyl 1,3-dioxanium more difficult than the formation of its 4,6-dibenzyl counterpart, explaining the results we previously obtained in our CEST-NMR studies. 29,41 The identified lowest energy conformers of the dioxanium and oxocarbenium cations were subsequently used to compute reference IR-spectra to aid in interpretation of the experimentally obtained spectra. 26,42 Figure 1a,b shows the computed spectra (filled) and the experimental spectra (black line) to confirm the formation of the dioxanium ions, as indicated by a characteristic dioxanium −[C−O] + stretch (∼1550 cm −1 ) and the absence of the oxocarbenium [C1� O5] + (∼1565 cm −1 ) and benzoyl C�O (∼1775 cm −1 ) stretches.…”
Section: ■ Results and Discussionmentioning
confidence: 99%
“…The formation of the two different reactive intermediates accounts well for the dichotomy in the stereochemical outcome for the 3-O-benzoyl benzylidene mannose and glucose systems. The mannosyl dioxanium ion, detected by 13 C CEST NMR, 29,41,45 is responsible for the stereoselective formation of the α-mannosyl glycosylation products. In contrast, the glucosyl 1,3-dioxanium ion could be formed and characterized in the gas phase, but no evidence was found in solution.…”
Section: ■ Results and Discussionmentioning
confidence: 99%
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