N(OMe) disaccharide analogs, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy- 6-methoxyamino-α-D-glucopyranoside in aqueous environment. The coupling reactions were found to be chemo and stereoselective affording β-(1-6) disaccharide mimics when using Glc and GlcNAc, in the case of Gal the β-anomer was prevalent (β:α = 7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogs was shown, based on the use of unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds has been carried out using NMR, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe) analogs exhibit a slightly different conformational behavior compared to their parent natural disaccharides.

Peri, F., Jiménez Barbero, J., García Aparicio, V., Tvaroska, I., & Nicotra, F. (2004). Synthesis and conformational analysis of novel N(OCH3) disaccharide analogues. CHEMISTRY-A EUROPEAN JOURNAL, 10(6), 1433-1444 [10.1002/chem.200305587].

Synthesis and conformational analysis of novel N(OCH3) disaccharide analogues

PERI, FRANCESCO;NICOTRA, FRANCESCO
2004

Abstract

N(OMe) disaccharide analogs, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy- 6-methoxyamino-α-D-glucopyranoside in aqueous environment. The coupling reactions were found to be chemo and stereoselective affording β-(1-6) disaccharide mimics when using Glc and GlcNAc, in the case of Gal the β-anomer was prevalent (β:α = 7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogs was shown, based on the use of unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds has been carried out using NMR, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe) analogs exhibit a slightly different conformational behavior compared to their parent natural disaccharides.
Articolo in rivista - Articolo scientifico
Scientifica
Carbohydrates; Conformational analysis; Glycosylation; NMR spectroscopy
English
Peri, F., Jiménez Barbero, J., García Aparicio, V., Tvaroska, I., & Nicotra, F. (2004). Synthesis and conformational analysis of novel N(OCH3) disaccharide analogues. CHEMISTRY-A EUROPEAN JOURNAL, 10(6), 1433-1444 [10.1002/chem.200305587].
Peri, F; Jiménez Barbero, J; García Aparicio, V; Tvaroska, I; Nicotra, F
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/10281/26972
Citazioni
  • Scopus 55
  • ???jsp.display-item.citation.isi??? 51
Social impact