符合性分析探讨了在选择性化环素中静电非经典CF···HC结相互作用的作用
Mengfan He1, Bruno A Piscelli2, Rodrigo A Cormanich2
1School of Chemistry, Biomedical Sciences Research Complex, University of St Andrews, North Haugh, St Andrews, Fife KY16 9ST, United Kingdom.
化环素由于非经典的结,表现出意想不到的轴向偏好. 本研究使用各种化环素的计算和实验方法来探索这些构造平衡.
科学领域:
- 有机化学 有机化学
- 计算化学计算化学
- 物理化学 物理化学
背景情况:
- 环素衍生物通常偏好于赤道替代剂.
- 化显著改变电子特性和形状偏好.
- 了解基环素构造对于预测化学行为至关重要.
研究的目的:
- 为了研究选择性化环素的结构平衡.
- 为了确定和其他素对环素构成的影响.
- 阐明这些偏好驱动的潜在机制,例如非经典的键.
主要方法:
- 可变温度核磁共振 (VT-NMR) 光谱仪用于实验分析.
- 计算化学,特别是M06-2X/aug-cc-pVTZ级别的计算.
- 自然键轨道 (NBO) 分析以分解电子效应.
主要成果:
- 1,1,4,-三环素 (7) 意外地更喜欢轴形状 (ΔG = 1.06 kcal mol−1).
- 高化环素 (9) 显示出更强的轴向偏好 (ΔG = 2.73 kcal mol−1).
- 和轴之间的非经典键 (NCHB) 显著导致观察到的轴偏差.
结论:
- 化可以取代循环素的典型形状偏好,有利于轴状排列.
- 非经典的键是这些化系统的构造行为的一个关键因素.
- 在伪单元位上的素的静电极化会影响调节器的稳定性,即使没有NCHB.
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