Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study
Abstract
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 effectSource:
Computational and Theoretical Chemistry, 2015, 1051, 104-109Publisher:
- Elsevier
Funding / projects:
DOI: 10.1016/j.comptc.2014.11.004
ISSN: 2210-271X
WoS: 000347862000013
Scopus: 2-s2.0-84919343344
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Institution/Community
IHTMTY - JOUR AU - Vitnik, Željko AU - Fabian, Walter M F PY - 2015 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1746 AB - 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). PB - Elsevier T2 - Computational and Theoretical Chemistry T1 - Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study VL - 1051 SP - 104 EP - 109 DO - 10.1016/j.comptc.2014.11.004 ER -
@article{ author = "Vitnik, Željko and Fabian, Walter M F", year = "2015", abstract = "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).", publisher = "Elsevier", journal = "Computational and Theoretical Chemistry", title = "Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study", volume = "1051", pages = "104-109", doi = "10.1016/j.comptc.2014.11.004" }
Vitnik, Ž.,& Fabian, W. M. F.. (2015). Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study. in Computational and Theoretical Chemistry Elsevier., 1051, 104-109. https://doi.org/10.1016/j.comptc.2014.11.004
Vitnik Ž, Fabian WMF. Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study. in Computational and Theoretical Chemistry. 2015;1051:104-109. doi:10.1016/j.comptc.2014.11.004 .
Vitnik, Željko, Fabian, Walter M F, "Ring- and side-group conformational properties of di-O-acylated xylopyranosides: A computational study" in Computational and Theoretical Chemistry, 1051 (2015):104-109, https://doi.org/10.1016/j.comptc.2014.11.004 . .