Castro-Fernández Silvia, Yang Ren, García A Patricio, Garzón Ignacio L, Xu Hai, Petrovic Ana G, Alonso-Gómez J Lorenzo
Departamento de Química Orgánica, Universidade de Vigo, Lagoas-Marcosende s/n, Vigo, 36310, Spain.
College of Chemistry and Chemical Engineering, Central South University, 932 Lushan S Rd, Yuelu, Changsha, Hunan, P. R. China.
Chemistry. 2017 Sep 4;23(49):11747-11751. doi: 10.1002/chem.201702986. Epub 2017 Aug 7.
State-of-the-art chiroptical spectroscopies are valuable tools for structural elucidation. However, the potential of these spectroscopies for everyday applications has not been exploited to date partially due to the lack of sufficiently stable and efficient chiroptical systems. To this end, the development of suitable chiroptical structures is essential. Herein, we present the synthesis of spiro-compounds (P )-1 and (P )-2 as well as (M )-1 and (M )-2 exhibiting remarkable chiroptical responses. Theoretical simulations show that (P )-1, constituted by two (P)-configured spiranic chiral axes, presents an all-carbon double helix structure with (M)-helicity. On the other hand, molecular dynamic simulations reveal (P )-2 to have a single path for geometry-modification along its flat conformational space, certifying it as a chiral flexible shape-persistent macrocycle. Geometric quantification of chirality has been used to compare the spiranic derivatives presented herein.
最先进的圆二色光谱技术是用于结构解析的宝贵工具。然而，这些光谱技术在日常应用中的潜力迄今尚未得到充分发掘，部分原因是缺乏足够稳定和高效的圆二色系统。为此，开发合适的圆二色结构至关重要。在此，我们展示了螺环化合物（P）-1和（P）-2以及（M）-1和（M）-2的合成，它们表现出显著的圆二色响应。理论模拟表明，由两个（P）构型的螺环手性轴构成的（P）-1呈现出具有（M）螺旋性的全碳双螺旋结构。另一方面，分子动力学模拟显示（P）-2在其平面构象空间中有一条用于几何形状修饰的单一路径，证明它是一种手性柔性形状持久大环。已使用手性的几何量化来比较本文所呈现的螺环衍生物。
