Exploring Conformational Preferences in XC(W)ZY Molecules With X, Y = F, Cl, Br and W, Z = O, S, Se: Unraveling the Influence of Conjugative and Anomeric Interactions

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano
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引用次数: 0

Abstract

The relative stabilities of the syn- and anti-conformers of 72 molecules belonging to the XC(W)ZY type, with X, Y = F, Cl, Br and W, Z = O, S, Se, have been computed using the B3LYP/aug-cc-pVDZ approximation. The conformational preferences, represented by the energy differences between the two rotamers, exhibit a systematic trend in relation to both the halogen atoms and the chalcogen atoms. These computational predictions are in agreement with available experimental results. The NBO formalism was employed to assess the influence of both the conjugative and anomeric interactions on the relative energy of the conformers. It has been determined that the conjugative interaction provides a satisfactory explanation for the energy differences between rotamers. In contrast, the anomeric interactions favors the syn-conformation in all cases. The relative stabilities between XC(W)ZY/YC(W)ZX and XC(W)ZY/XC(Z)WY constitutional isomers have also been computed and correlated with the experimental data.

Abstract Image

探索 XC(W)ZY 分子中的构象偏好,其中 X、Y = F、Cl、Br 和 W、Z = O、S、Se:揭示共轭和同分异构相互作用的影响
采用 B3LYP/aug-cc-pVDZ 近似方法计算了 72 个 XC(W)ZY 型分子(X、Y = F、Cl、Br 和 W、Z = O、S、Se)的同构型和反构型的相对稳定性。由两个旋转体之间的能量差异所代表的构象优选性与卤素原子和查尔根原子的关系呈现出一种系统的趋势。这些计算预测与现有的实验结果一致。我们采用 NBO 形式来评估共轭作用和同分异构作用对构象相对能量的影响。结果表明,共轭作用可以令人满意地解释转构体之间的能量差异。相比之下,同分异构作用在所有情况下都有利于合成构象。此外,还计算了 XC(W)ZY/YC(W)ZX 和 XC(W)ZY/XC(Z)WY 构象异构体之间的相对稳定性,并将其与实验数据进行了关联。
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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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