Complications of modeling glycosylation reactions: can the anomeric conformation of a donor determine the glycopyranosyl oxacarbenium ring conformation?

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DOIResolve DOI: http://doi.org/10.1016/j.carres.2012.04.001
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TypeArticle
Proceedings titleCarbohydrate Research
ConferenceThe XVI European Carbohydrate Congress, July 3-7, 2012, Sorrento, Italy
ISSN0008-6215
Volume356
Pages191195
SubjectGlycosylation; Anomeric conformation; Oxacarbenium ion; Pyranosyl ring conformation
AbstractThat the ring conformation of glycopyranosyl oxacarbenium ions can influence the stereochemical outcome of glycosylation reactions has been postulated for some time. Some new ionization calculations show that the ultimate conformation 4H3 or 5S1 of D-glucopyranosyl oxacarbenium ions depends on the initial ϕH (CH-1-C-1–S+-SCH3) conformation of anomeric thiosulfonium ions. Evidence is also presented that nucleophile:electrophile hydrogen bonded complexes, 1,6-anhydro-carbenium ions and electron rich carbon nucleophile:oxacarbenium ion complexes are all probably artifacts of neglecting counter ions or nucleophiles in the DFT calculation. All three cationic species are likely important for glycosylation reaction side reactions but not as productive species.
Publication date
LanguageEnglish
AffiliationHuman Health Therapeutics; National Research Council Canada
Peer reviewedNo
IdentifierS0008621512001668
NPARC number21268687
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Record identifier46efcb57-84aa-497e-bd6a-63c56a4780d8
Record created2013-11-07
Record modified2016-05-09
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