Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study
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The conformational properties (C-4(1), C-1(4), and skew ring structures, side chain torsion) of methyl 2,4-(1) and 3,4-O-diacetyl (2) as well as 2,4-(3) and 3,4-O-dibenzoyl (4)-SS-D-xylopyranoside are calculated by dispersion-corrected density functional theory (B3LYP-D3) and LPNO-CEPA/1-def2-TZVPP. Derivatives with acyl groups in positions 2 and 4 (1 and 3) prefer the 1C4 chair conformation of the pyranose chair; 3,4-di-O-acyl compounds 2 and 4 show nearly equal or even dominating amounts of the C-4(1) chair. Intramolecular hydrogen bonding of the type O3-H center dot center dot O1 (1 and 3) and O2-H center dot center dot center dot O4 are characteristic for the lowest energy conformations of 1C4 chairs. With increasing solvent polarity a shift towards 4C1 chair structures is calculated. B3LYP-D3 conformer populations show fairly good agreement with CEPA/1 results (R-2 = 0.992).
Keywords:Density functional / Dispersion correction / LPNO-CEPA/1 / Ring conformation / Substituent and solvent effect
Source:Computational and Theoretical Chemistry, 2015, 1051, 104-109
- Elsevier Science Bv, Amsterdam