Díaz Jimena E, Mazzanti Andrea, Orelli Liliana R, Mancinelli Michele
Department of Industrial Chemistry "Toso Montanari", University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy.
Departamento de Química Orgánica. Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires. CONICET, Junín 956, 1113 Buenos Aires, Argentina.
ACS Omega. 2019 Mar 4;4(3):4712-4720. doi: 10.1021/acsomega.9b00192. eCollection 2019 Mar 31.
The stereodynamic behavior of 1-arylpyrrolidin-2-imines, having a C-N stereogenic axis, has been studied by means of dynamic nuclear magnetic resonance and density functional theory calculations, evaluating the steric effect of -aryl substituents. The rotational barrier due to / isomerism about the -C=N-H bond was also determined. The dynamic stereochemistry of homologous six- and seven-membered iminoazacycloalkane rings and their oxo-analogues was also comparatively investigated, evidencing a ring size effect. It was found that the seven-membered heterocycle shows additional dynamic features because of ring inversion.
通过动态核磁共振和密度泛函理论计算，研究了具有C-N立体异构轴的1-芳基吡咯烷-2-亚胺的立体动力学行为，评估了芳基取代基的空间效应。还确定了由于-C=N-H键的E/Z异构化引起的旋转势垒。还对同源的六元和七元亚氨基氮杂环烷环及其氧代类似物的动态立体化学进行了比较研究，证明了环大小效应。结果发现，七元杂环由于环翻转而表现出额外的动态特征。
