An attempt to consider cooperativity in helical-sense preferences induced in fused macrocycles
An attempt to consider cooperativity in helical-sense preferences induced in fused macrocycles
复制标题
尝试考虑稠合大环中诱导的螺旋方向偏好的协同性
DOI：
10.1039/d3ob00171g
复制
发表时间：
2023
影响因子：
3.2
通讯作者：
Kawai Shunsuke
中科院分区：
文献类型：
--
作者：
Katoono Ryo;Kudo Takaaki;Kawai Shunsuke
我们合成了双和三（大环），其中两个或三个重大环稠合，并且各自采用具有M-或P-螺旋性的扭曲形式。根据每个元素的扭曲方向，分子中可以产生不同的构象。我们提出两种类型的构象偏好。一是对整个分子具有相同扭曲感的螺旋形式的天生偏好。另一个是螺旋感对特定扭曲感的偏好。我们对 Kn 和 (K1)n 之间的关系感兴趣，其中 Kn 是两种螺旋形式（MM 和 PP、MMM 和 PPP）之间构象相互转化的平衡常数，n 是元素的数量，因为我们认为这种关系可以作为衡量单个分子中这些大环元素之间相互影响的度量。通过 1H NMR 和 CD 光谱中的 VT 测量，我们尝试量化稠合大环（n = 2 和 3）中诱导的螺旋方向偏好，以比较 Kn 和 (K1)n。
We synthesized bis and tris(macrocycle)s in which a two- or three-fold macrocycle was fused and each adopted twisted forms with M- or P-helicity. According to the sense of twisting in each element, diverse conformations can be generated in a molecule. We present two types of conformational preferences. One is the innate preference for a helical form with an identical sense of twisting throughout the entire molecule. The other is the helical-sense preference for a particular sense of twisting. We were interested in the relationship between Kn and (K1)n, where Kn is an equilibrium constant for the conformational interconversion between two helical forms (MM and PP, MMM and PPP) and n is the number of elements, since we considered that the relationship could be a metric to see the interinfluence among these macrocyclic elements in a single molecule. Through VT measurements in 1H NMR and CD spectroscopy, we attempted to quantify the helical-sense preferences induced in the fused macrocycles (n = 2 and 3) to compare Kn and (K1)n.