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Title

Hydrogen Atom Transfer Experiments Provide Chemical Evidence for the Conformational Differences between C- and O-Disaccharides

AuthorsLeón, Elisa I. ; Martín, Ángeles ; Pérez-Martín, Inés ; Quintanal, Luis M.; Suárez, Ernesto
KeywordsCarbohydrates
Disaccharides
Conformation analysis
Radical reactions
Hydrogen transfer
Issue Date1-Sep-2010
PublisherWiley-VCH
CitationEuropean Journal of Organic Chemistry 27: 5248-5262 (2010)
AbstractThe glycopyran-6-O-yl radical promoted hydrogen atom transfer reaction (HAT) between the two pyranose units of ¿-D-Manp-(1-4)-¿-D-Glcp and ¿-D-Manp-(1-4a)-4a-carba-¿-D-Glcp disaccharides provides supporting chemical evidence for the conformational differences between O- and C-glycosyl compounds. In the O-disaccharide the 6-alkoxyl radical, generated under oxidative or reductive conditions, abstracts exclusively the hydrogen at C-5' via a completely regioselective 1,8-HAT reaction. This may be attributable to the conformational restriction of the glycosidic and aglyconic bonds due principally to steric and stereoelectronic effects. On the contrary, very little regioselectivity is observed in the homologous C-disaccharide and a mixture of compounds generated by 1,5-, 1,6-, and 1,8-HAT processes where the abstraction occurs at hydrogen atoms positioned at C-4a, C-1', and C-5', respectively, has been obtained. This study has been extended to simpler O- and C-glycosides, where the aglycon was a straight n-alkyl alcohol tether of five atoms; in general, all of the results obtained are shown to be consistent with a major conformational flexibility of the C-glycosidic bond.
Publisher version (URL)http://dx.doi.org/10.1002/ejoc.201000470
URIhttp://hdl.handle.net/10261/205166
Identifiersdoi: 10.1002/ejoc.201000470
issn: 1434-193X
e-issn: 1099-0690
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