Stereoelectronic effects of substituents at O-2 on glycosylation reactions

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Proceedings titleProceedings, 239th ACS National Meeting, San Francisco, CA
Conference239th ACS National Meeting & Exposition American Chemical Society Meeting, March 21-25, 2010; San Francisco, CA, USA
Abstract[During density functional theory (DFT) studies of glycopyranosyl oxacarbenium ions two unexpected conformational preferences for substituents at O-2 were discovered. One is that substituents at O-2 have a propensity to be equatorial. This leads to a unexpected stability of the 5S1 conformer of D-glucopyranosyl oxacarbenium ions. The second is for the first atom attached to O-2 to adopt a syn conformation. This was shown to be a result of hyperconjugation between a lone pair on O-2 and the LUMO associated with the C-1--O-5 double bond. In order to provide experimental corroboration we have prepared glucopyranosyl donors with a chiral methyl cyclopropylmethyl group at O-2. The results of glycosylation reactions with 4 glycosyl acceptors of these donors will be presented. As well, the conformational preferences of the associated glucopyranosyl oxacarbenium ions as determined by DFT calculations will be presented]>
Publication date
PublisherAmerican Chemical Society
AffiliationNRC Institute for Biological Sciences; National Research Council Canada
Peer reviewedYes
NPARC number17438027
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Record identifierb450c2d4-ff3c-4722-8157-2b5c7bab59fa
Record created2011-04-05
Record modified2016-08-23
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