An investigation of the pyranose ring interconversion path of α-L-idose calculated using density functional theory
An investigation of the pyranose ring interconversion path of α-L-idose calculated using density functional theory
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DOI：
10.1016/j.carres.2006.07.015
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发表时间：
2006-11-06
影响因子：
3.1
通讯作者：
Ueda, Kazuyoshi
中科院分区：
文献类型：
--
作者：
Kurihara, Youji;Ueda, Kazuyoshi
使用密度泛函计算研究了α-L-艾糖的吡喃糖环构象从C-4(1)椅到其他构象的相互转化途径。从这些计算中，获得了四种不同的环互变路径及其从C-4(1)椅到其他构象，例如B-3、B-O和S-1(3)的过渡态结构。这四种过渡态构象涵盖了羟基氢键网络模式（顺时针和逆时针）和伯醇基团构象（tg和gg）的四种可能的组合。优化的构象、过渡态及其内在反应坐标 (IRC) 均在 B3LYP/6-31G** 水平上计算。获得的结构之间的能量差异在B3LYP/6-311++G**水平上进行评估。优化构象表明，C-4(1)、S-2(O)和B-3、B-O构象异构体具有相似的能量，而S-1(3)构象异构体的能量高于其他构象异构体。使用 IRC 计算确认的四种过渡态及其环互变路径的比较表明，α-L-吡喃糖环最可能的环互变发生在通过 E-3 包络线的 C-4(1) 和 B-3,B-O 之间，其中涉及 5.21 kcal/mol 的能垒。 (c) 2006 Elsevier Ltd. 保留所有权利。
The interconversion pathways of the pyranose ring conformation Of alpha-L-idose from a C-4(1) chair to other conformations were investigated using density functional calculations. From these calculations, four different ring interconversion paths and their transition state structures from the C-4(1) chair to other conformations, such as B-3,B-O, and S-1(3), were obtained. These four transition-state conformations cover four possible combinations of the network patterns of the hydroxyl group hydrogen bonds (clockwise and counterclockwise) and the conformations of the primary alcohol group (tg and gg). The optimized conformations, transition states, and their intrinsic reaction coordinates (IRC) were all calculated at the B3LYP/6-31G** level. The energy differences among the structures obtained were evaluated at the B3LYP/6-311++G** level. The optimized conformations indicate that the conformers of C-4(1), S-2(O), and B-3,B-O have similar energies, while S-1(3) has a higher energy than the others. The comparison of the four transition states and their ring interconversion paths, which were confirmed using the IRC calculation, suggests that the most plausible ring interconversion of the alpha-L-idopyranose ring occurs between C-4(1) and B-3,B-O through the E-3 envelope, which involves a 5.21 kcal/mol energy barrier. (c) 2006 Elsevier Ltd. All rights reserved.