Department of Chemistry, Federal University of Lavras, P.O. Box 3037, 37200-000, Lavras, MG, Brazil.
Beilstein J Org Chem. 2012;8:1227-32. doi: 10.3762/bjoc.8.137. Epub 2012 Aug 2.
Four diastereoisomers of 2-fluorobicyclo[2.2.1]heptan-7-ols were computationally investigated by using quantum-chemical calculations, and their relative energies were analyzed on the basis of stereoelectronic interactions, particularly the presence or otherwise of the F∙∙∙HO intramolecular hydrogen bond in the syn-exo isomer. It was found through NBO and AIM analyses that such an interaction contributes to structural stabilization and that the (1h)J(F,H(O)) coupling constant in the syn-exo isomer is modulated by the n(F)→σ*(OH) interaction, i.e., the quantum nature of the F∙∙∙HO hydrogen bond.
使用量子化学计算对 2-氟双环[2.2.1]庚烷-7-醇的 4 种非对映异构体进行了计算研究，并基于立体电子相互作用（特别是在顺式-外消旋异构体中是否存在 F∙∙∙HO 分子内氢键）分析了它们的相对能量。通过 NBO 和 AIM 分析发现，这种相互作用有助于结构稳定，并且顺式-外消旋异构体中的 (1h)J(F,H(O)) 偶合常数受到 n(F)→σ*(OH) 相互作用的调制，即 F∙∙∙HO 氢键的量子性质。
