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Origin of anomeric effect: A density functional steric analysis

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成果类型:
期刊论文
作者:
Huang, Ying;Zhong, Ai-Guo;Yang, Qinsong;Liu, Shubin
通讯作者:
Liu, S.(shubin@email.unc.edu)
作者机构:
[Zhong, Ai-Guo] Department of Chemistry, Taizhou College, Linhai Zhejiang 317000, China
[Yang, Qinsong] PT TSG Chemical, Jl. Inspeksi Kalimalang, Sukadanau, Cikarang Barat, Lokasi G II, Sektor 3, Bekasi 17520, Indonesia
[Liu, Shubin] Research Computing Center, University of North Carolina, Chapel Hill, NC 27599-3420, United States
[Huang, Ying] School of Pharmacy, Hunan University of Chinese Medicine, Changsha, Hunan 410208, China
通讯机构:
[Liu, Shubin] Univ N Carolina, Ctr Res Comp, Chapel Hill, NC 27599 USA.
语种:
英文
关键词:
A-density - Anomeric effect - Axial orientations - Conformational space - Cyclohexane ring - D-glucopyranose - Density functionals - Electrostatic interactions - Energy components - Energy differences - Equatorial positions - Exchange-correlations - Heteroatoms - Hyperconjugation effects - Steric hindrances - Strong correlation - Total energy differences - Two-component
期刊:
The Journal of chemical physics
ISSN:
0021-9606
年:
2011
卷:
134
期:
8
页码:
084103
文献类别:
WOS:Article;EI:Journal article (JA)
所属学科:
ESI学科类别:化学;WOS学科类别:Chemistry, Physical;Physics, Atomic, Molecular & Chemical
入藏号:
WOS:000287811300006;EI:20110913714282;PMID:21361523
基金类别:
Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences, U. S. Department of Energy (DOE) [DE-FG02-06ER15788]; U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences [DE-SC0001011]
机构署名:
本校为第一机构
院系归属:
药学院
摘要:
The anomeric effect (the tendency of heteroatomic substituents adjacent to a heteroatom within the cyclohexane ring to prefer the axial orientation instead of the sterically less hindered equatorial position) is traditionally explained through either the dipole moment repulsion or the hyperconjugation effect. In this work, by employing our recent work in density functional steric analysis, we provide a novel two-component explanation, which is consistent with the common belief in chemistry that the effect has a stereoelectronic origin. With alpha-D-glucopyranose as the prototype, we systematically explore its conformational space and generate 32 isomers, leading to a total of 80 axial-equatorial conformation pairs. The energy difference analysis of these pairs shows that while statistically speaking the tendency is valid, the anomeric effect is not always true and can be violated. Three energy components, exchange-correlation, classical electrostatic, and density functional steric, are found to be directly proportional to the total energy difference between axial and equatorial isomers. We also found that the total dipole moment change, not the hyperconjugation effect, is a reasonable indicator of the total energy difference. However, all these correlations alone are not strong enough to provide a compellingly convincing explanation for the general validity of the effect. With the help of strong correlations between energy components, an explanation with two energy components, steric and electrostatic, was proposed in this work. We show that the axial-equatorial energy difference in general, with the anomeric effect as a special case, is dictated by two factors of the stereoelectronic origin, steric hindrance and classical electrostatic interactions, synchronously working together. Another explanation in terms of exchange-correlation and electrostatic interactions has also been obtained in this work. (C) 2011 American Institute of Physics. [doi:10.1063/1.3555760]
参考文献:
Badenhoop JK, 1997, J CHEM PHYS, V107, P5406, DOI 10.1063/1.474248
Bader R. F. W., 1990, ATOMS MOL QUANTUM TH
BECKE AD, 1993, J CHEM PHYS, V98, P1372, DOI 10.1063/1.464304
Box VGS, 2000, J MOL STRUCT, V522, P145, DOI 10.1016/S0022-2860(99)00358-0
CRAMER CJ, 1992, J ORG CHEM, V57, P7034, DOI 10.1021/jo00052a012

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