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Abstract:

In a previous paper (Bohn et al., Carbohydr. Res., 2007, 342, 2522) the relative O3/O4 reactivities of both α- and β-methyl glycosides of N-dimethylmaleoyl (DMM) glucosamine acceptors protected at O6 with three different groups were assessed by us, using two glycosyl donors. The α-anomers showed preferential or exclusive substitution at O3, whereas the β-anomers gave preferential or exclusive substitution at O4. A DFT study of analogs of the reported acceptors indicates that whereas the β-anomers carry the DMM ring parallel to the C2-H2 bond for steric reasons, the α-anomers tilt this ring producing a strong hydrogen bond between the H(O)3 and one of the DMM carbonyl groups. In this way, the O3 group becomes more nucleophilic and thus more reactive: both charge and Fukui functions on O3 and O4 in the model compounds support the experimental results. Surprisingly, the previously mentioned hydrogen bond is not the only driving force for the slant of the DMM group: the axial methoxyl group of the α-anomers also plays a role. The ease of rotation around the C2-N2 bond for DMM-protected analogs was assessed with different models. MP2 calculations using higher basis sets yield similar relative energy and charge values to those calculated using DFT. © The Royal Society of Chemistry 2008.

Registro:

Documento: Artículo
Título:Conformational and electronic effects on the regioselectivity of the glycosylation of different anomers of N-dimethylmaleoyl-protected glucosamine acceptors
Autor:Bohn, M.L.; Colombo, M.I.; Rúveda, E.A.; Stortz, C.A.
Filiación:Instituto de Química Orgánica y de Síntesis (CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Suipacha 531, 2000, Rosario, Argentina
Departamento de Química Orgánica-CIHIDECAR, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Pab. 2, 1428, Buenos Aires, Argentina
Palabras clave:Aromatic polymers; Conformations; Electronic structure; Glycosylation; Regioselectivity; Substitution reactions; Glycosyl donors; N-dimethylmaleoyl (DMM) glucosamine acceptors; Amines; drug derivative; glucosamine; oxygen; article; chemical structure; chemistry; conformation; electron; enzyme specificity; glycosylation; hydrogen bond; mechanical torsion; metabolism; nomenclature; rotation; stereoisomerism; thermodynamics; Carbohydrate Conformation; Electrons; Glucosamine; Glycosylation; Hydrogen Bonding; Models, Molecular; Oxygen; Rotation; Stereoisomerism; Substrate Specificity; Terminology as Topic; Thermodynamics; Torsion, Mechanical
Año:2008
Volumen:6
Número:3
Página de inicio:554
Página de fin:561
DOI: http://dx.doi.org/10.1039/b715847e
Título revista:Organic and Biomolecular Chemistry
Título revista abreviado:Org. Biomol. Chem.
ISSN:14770520
CAS:glucosamine, 3416-24-8, 4607-22-1; oxygen, 7782-44-7; Glucosamine, 3416-24-8; Oxygen, 7782-44-7
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14770520_v6_n3_p554_Bohn

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Citas:

---------- APA ----------
Bohn, M.L., Colombo, M.I., Rúveda, E.A. & Stortz, C.A. (2008) . Conformational and electronic effects on the regioselectivity of the glycosylation of different anomers of N-dimethylmaleoyl-protected glucosamine acceptors. Organic and Biomolecular Chemistry, 6(3), 554-561.
http://dx.doi.org/10.1039/b715847e
---------- CHICAGO ----------
Bohn, M.L., Colombo, M.I., Rúveda, E.A., Stortz, C.A. "Conformational and electronic effects on the regioselectivity of the glycosylation of different anomers of N-dimethylmaleoyl-protected glucosamine acceptors" . Organic and Biomolecular Chemistry 6, no. 3 (2008) : 554-561.
http://dx.doi.org/10.1039/b715847e
---------- MLA ----------
Bohn, M.L., Colombo, M.I., Rúveda, E.A., Stortz, C.A. "Conformational and electronic effects on the regioselectivity of the glycosylation of different anomers of N-dimethylmaleoyl-protected glucosamine acceptors" . Organic and Biomolecular Chemistry, vol. 6, no. 3, 2008, pp. 554-561.
http://dx.doi.org/10.1039/b715847e
---------- VANCOUVER ----------
Bohn, M.L., Colombo, M.I., Rúveda, E.A., Stortz, C.A. Conformational and electronic effects on the regioselectivity of the glycosylation of different anomers of N-dimethylmaleoyl-protected glucosamine acceptors. Org. Biomol. Chem. 2008;6(3):554-561.
http://dx.doi.org/10.1039/b715847e