碳卤键的超共轭相互作用影响环状α-卤代缩醛的几何形状。
Hyperconjugative Interactions of the Carbon-Halogen Bond that Influence the Geometry of Cyclic α-Haloacetals.
机构信息
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
出版信息
J Org Chem. 2022 Apr 15;87(8):5315-5327. doi: 10.1021/acs.joc.2c00148. Epub 2022 Apr 1.
Abstract
The analysis of the structures of low-energy conformers of different α-haloacetals reveals changes in bond lengths and geometries that correspond to stabilizing orbital interactions that contribute to the ground-state structures of these systems. Several factors, including the electron-donating and electron-accepting abilities of the substituents on the ring, affect the degree of the electronic interactions in these carbohydrate-like systems. The presence of an α-halogen atom that can participate in hyperconjugation has been shown to contribute to the structural characteristics of the low-energy conformer. The experimental evidence is supported by natural bond order (NBO) analysis to identify the types of interactions and to assess their relative importance.
摘要
对不同 α-卤代乙缩醛低能构象异构体结构的分析揭示了键长和几何形状的变化，这些变化对应于稳定轨道相互作用，有助于这些体系的基态结构。包括环上取代基的供电子和吸电子能力在内的几个因素，影响了这些类似碳水化合物体系中电子相互作用的程度。已经表明，能够参与超共轭的α-卤原子的存在有助于低能构象异构体的结构特征。自然键轨道（NBO）分析支持实验证据，以确定相互作用的类型并评估它们的相对重要性。
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