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| - Exploring the Mechanism of Neighboring Group AssistedGlycosylation Reactions
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| Abstract
| - Glycosyl donors based on the 2,6-di-O-acyl-3,4-O-isopropylidene-d-galactopyranosyl-(leaving group)structure have been shown experimentally to have a high propensity for giving acyl transfer to the alcoholnucleophile as major side products in the glycosylation reaction. The corresponding cations of these relativelyrigid glycosyl donors were investigated by density functional methods. The precursor cations resulting fromneighboring group assistance from the 2-O-acyl group were found to be the most stable. The nucleophilemethanol most favorably approaches the LUMO of such cations on the former carbonyl carbon. The resultingstable intermediate has a long C−O bond of 2.79 Å. It is suggested that such intermediates can lead to bothacyl transfer and β-glycoside after passing through at least one further transition state.
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