Chirality Gearing in an Achiral Cage through Adaptive Binding
Chirality Gearing in an Achiral Cage through Adaptive Binding
复制标题
通过自适应结合在非手性笼中实现手性传动
DOI：
10.1021/jacs.2c02040
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发表时间：
2022-04-13
影响因子：
15
通讯作者：
Wang, Qi-Qiang
中科院分区：
文献类型：
--
作者：
Hu, Qi-Ping;Zhou, Hao;Wang, Qi-Qiang
本文报道了一种自适应的非手性三硫脲分子笼及其与三羧酸阴离子结合的构象和立体动力学.笼的合成简单，四步反应产率为44%。它具有灵活的构象，与1，3，5-苯三甲酸形成一种类包合物，在乙腈中的亲和力可达106 M-1。在结合时，笼被锁定在扭曲的螺旋构象中。通过在客体上引入三个手性臂，产生了在一个特定螺旋方向上占优势的齿轮状配合物。由于螺旋槽中的空间拥挤，客体分子上甲基到乙基的微小变化导致了结合和手性诱导的显著差异。因此，该系统代表了一个罕见的例子，手性诱导的柔性，非手性主体，并提供了一个解耦的模型，产生的外消旋体和随后的手性歧视，可以单独探测
Herein we report an adaptive, achiral trithiourea molecular cage and its conformational and stereodynamics towardtricarboxylate anion binding. The cage was readily synthesized in four steps with a 44% yield for the irreversible cage-formingreaction. It possesses aflexible conformation and strongly binds 1,3,5-benzene tricarboxylate by forming a sandwich-like inclusioncomplex, with an affinity up to 106M-1in acetonitrile. Upon binding, the cage is locked in a twisted helical conformation. Byincorporation of three chiral arms on the guest, a gear-like complex dominant in one given helical sense was produced. Due to thesteric crowding in the helical grooves, a small change of methyl to ethyl on guest caused a striking difference on binding and chiralinduction. The system thus represents a rare example of chiral induction on aflexible, achiral host and provides a decoupled modelthat the generation of a racemate and following chiral discrimination can be individually probed