The conformational behavior of methyl (2-acetamido-2-deoxy-α-d- mannopyranosyl)phosphate 1, and its analogues, methyl C-(2-acetamido-2-deoxy- α-d-mannopyranosyl)methanephosphonate 2 and methyl O-(2-acetamido-2-deoxy- 5a-carba-α-d-mannopyranosyl)phosphate 3, where a methylene group replaces, respectively, the anomeric and the pyranose oxygen atom, was investigated at the B3LYP/6-311+G(d,p) level [6-311+G(2df,p) for the phosphorus atom]. The energy of the optimized structures was recalculated using the continuum solvent model C-PCM choosing water as the solvent. The compounds exhibited several populated conformations, but they all showed a marked preference for the 4C1 geometry of the pyranose ring; this preference was almost complete for 1, very large for the phosphono analogue 2, and large for the carba analogue 3. To give experimental support to these results, compounds 2 and 3 were synthesized and characterized by NMR spectroscopy. The comparison of the theoretical and experimental vicinal coupling constants confirmed the marked preference for the 4C1 geometry in the case of 2 and suggested that the same holds true for compound 3.

Toma, L., Legnani, L., Rencurosi, A., Poletti, L., Lay, L., Russo, G. (2009). Modeling of synthetic phosphono and carba analogues ofN-acetyl-alpha-D-mannosamine 1-phosphate, the repeating unit of the capsular polysaccharide from Neisseria meningitidis serovar A. ORGANIC & BIOMOLECULAR CHEMISTRY, 7(18), 3734-3740 [10.1039/b907000a].

Modeling of synthetic phosphono and carba analogues ofN-acetyl-alpha-D-mannosamine 1-phosphate, the repeating unit of the capsular polysaccharide from Neisseria meningitidis serovar A

LEGNANI, LAURA;
2009

Abstract

The conformational behavior of methyl (2-acetamido-2-deoxy-α-d- mannopyranosyl)phosphate 1, and its analogues, methyl C-(2-acetamido-2-deoxy- α-d-mannopyranosyl)methanephosphonate 2 and methyl O-(2-acetamido-2-deoxy- 5a-carba-α-d-mannopyranosyl)phosphate 3, where a methylene group replaces, respectively, the anomeric and the pyranose oxygen atom, was investigated at the B3LYP/6-311+G(d,p) level [6-311+G(2df,p) for the phosphorus atom]. The energy of the optimized structures was recalculated using the continuum solvent model C-PCM choosing water as the solvent. The compounds exhibited several populated conformations, but they all showed a marked preference for the 4C1 geometry of the pyranose ring; this preference was almost complete for 1, very large for the phosphono analogue 2, and large for the carba analogue 3. To give experimental support to these results, compounds 2 and 3 were synthesized and characterized by NMR spectroscopy. The comparison of the theoretical and experimental vicinal coupling constants confirmed the marked preference for the 4C1 geometry in the case of 2 and suggested that the same holds true for compound 3.
Articolo in rivista - Articolo scientifico
Sugar analogues; DFT calculations; Capsular polysaccharides;
English
3734
3740
7
Toma, L., Legnani, L., Rencurosi, A., Poletti, L., Lay, L., Russo, G. (2009). Modeling of synthetic phosphono and carba analogues ofN-acetyl-alpha-D-mannosamine 1-phosphate, the repeating unit of the capsular polysaccharide from Neisseria meningitidis serovar A. ORGANIC & BIOMOLECULAR CHEMISTRY, 7(18), 3734-3740 [10.1039/b907000a].
Toma, L; Legnani, L; Rencurosi, A; Poletti, L; Lay, L; Russo, G
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/351890
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