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Abstract:

Both anomers of the methyl glycoside of 6-O-benzyl-N-dimethylmaleoyl-d- allosamine (6 and 7) are glycosylated exclusively on O3 when reacting with the trichloroacetimidate of peracetylated α-d-galactopyranose (5). This regioselectivity is expected for 6, the α-anomer, as a strong hydrogen bond of its H(O)3 with the carbonyl group of the dimethylmaleoyl group occurs, as shown by NMR temperature dependence. However, this hydrogen bond was not encountered experimentally for 7, the β-anomer. A DFT study of the energies implied in an analog of the glycosylation reaction charged intermediate has explained neatly this behavior, in terms of strong hydrogen bonds occurring at these charged intermediates. This approach explains both the experimental regioselectivities found for 6 and 7, but furthermore the calculations have shown a marked agreement with the regioselectivities found for other related compounds in the literature. © 2011 The Royal Society of Chemistry.

Registro:

Documento: Artículo
Título:Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
Autor:Colombo, M.I.; Rúveda, E.A.; Stortz, C.A.
Filiación:Instituto de Química Rosario (CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Suipacha 531 2000, Rosario, Argentina
Departamento de Química Orgánica-CIHIDECAR, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires, Argentina
Palabras clave:Anomers; Carbonyl groups; Charged intermediates; DFT study; Galactopyranose; Glycosylated; Glycosylation reactions; Methyl glycosides; Related compounds; Temperature dependence; Esterification; Glycosylation; Hydrogen; Reaction intermediates; Regioselectivity; Sugars; Hydrogen bonds; hexosamine; article; chemical structure; chemistry; Fourier analysis; glycosylation; methylation; Fourier Analysis; Glycosylation; Hexosamines; Methylation; Models, Molecular; Molecular Structure
Año:2011
Volumen:9
Número:8
Página de inicio:3020
Página de fin:3025
DOI: http://dx.doi.org/10.1039/c1ob00021g
Título revista:Organic and Biomolecular Chemistry
Título revista abreviado:Org. Biomol. Chem.
ISSN:14770520
CAS:Hexosamines
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14770520_v9_n8_p3020_Colombo

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Citas:

---------- APA ----------
Colombo, M.I., Rúveda, E.A. & Stortz, C.A. (2011) . Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach. Organic and Biomolecular Chemistry, 9(8), 3020-3025.
http://dx.doi.org/10.1039/c1ob00021g
---------- CHICAGO ----------
Colombo, M.I., Rúveda, E.A., Stortz, C.A. "Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach" . Organic and Biomolecular Chemistry 9, no. 8 (2011) : 3020-3025.
http://dx.doi.org/10.1039/c1ob00021g
---------- MLA ----------
Colombo, M.I., Rúveda, E.A., Stortz, C.A. "Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach" . Organic and Biomolecular Chemistry, vol. 9, no. 8, 2011, pp. 3020-3025.
http://dx.doi.org/10.1039/c1ob00021g
---------- VANCOUVER ----------
Colombo, M.I., Rúveda, E.A., Stortz, C.A. Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach. Org. Biomol. Chem. 2011;9(8):3020-3025.
http://dx.doi.org/10.1039/c1ob00021g