On the Influence of the C2−O2 and C3−O3 Bonds in 4,6-O-Benzylidene-Directed β-Mannopyranosylation and α-Glucopyranosylation
- 23 September 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 71 (22) , 8473-8480
- https://doi.org/10.1021/jo061417b
Abstract
The synthesis of 4,6-O-benzylidene-protected 2-deoxyarabino-, 3-deoxyarabino-, and 3-deoxyribothioglycosides is described and their glycosylation reactions, with activation by either 1-benzenesulfinyl piperidine/trifluoromethansulfonic anhydride or diphenyl sulfoxide/trifluoromethanesulfonic anhydride, studied. In contrast to the corresponding 4,6-O-benzylidene-protected glucosyl and mannosyl donors, which are α- and β-selective, respectively, poor diastereoselectivity is observed in all cases. The reasons for this poor selectivity are discussed in terms of the interaction between the C2−O2 and C3−O3 bonds in the glucosyl and mannosyl donors and of the influence of this interaction on the ease of formation of the intermediate glycosyl oxacarbenium ions.Keywords
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