Chiral diversification through the assembly of achiral phenylacetylene macrocycles with a two-fold bridge
Chiral diversification through the assembly of achiral phenylacetylene macrocycles with a two-fold bridge
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DOI：
10.1039/c9sc00972h
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发表时间：
2019-05-14
期刊：
影响因子：
8.4
通讯作者：
Suzuki, Takanori
中科院分区：
文献类型：
--
作者：
Katoono, Ryo;Kusaka, Keiichi;Suzuki, Takanori
我们展示了所谓的“手性多样化”，这是一种设计策略，通过组装和双桥的非手性组分，以创建多个手性分子。我们使用苯乙炔大环（PAM）作为非手性元素。在一个分子中，[6] PAM的两个非手性环一个堆叠在另一个之上，或者彼此机械结合。作为替代，[12] PAM的单个放大环也被假定为[6] PAM的双重形式。在任何情况下，一个或两个环通过共价键双桥连以发挥手性。通过分子内双键的形成，这些多个手性分子在一个反应中作为一组产物得到。在具有[6] PAM的两个螺旋堆叠环或[12] PAM的单个螺旋折叠环的分子中产生的动态手性通过借助于外部手性源的诱导Cotton效应来表征。因此，基于[12] PAM的手性结构可以被证明是第一次成功。另外，对于具有两个互锁环的[6] PAM分子，实现了对映体分离，显示出显着的手性性质。
We demonstrate so-called "chiral diversification", which is a design strategy to create multiple chiral molecules through the assembly and double-bridging of achiral components. We used phenylacetylene macrocycles (PAMs) as an achiral element. In a molecule, two achiral rings of [6] PAM are stacked one above the other, or bound to each other mechanically. As an alternative, a single enlarged ring of [12] PAM was also assumed to be a doubled form of [6] PAM. In any case, one or two ring(s) are doubly-bridged by covalent bonds to exert chirality. Through intramolecular two-bond formation, these multiple chiral molecules were obtained as a set of products in one reaction. The dynamic chirality generated in molecules with either two helically-stacked rings of [6] PAM or a single helically-folded ring of [12] PAM was characterized by induced Cotton effects with the aid of an external chiral source. Thus, a chiral structure based on [12] PAM could be demonstrated as the first success. Alternatively, enantiomeric separation was achieved for molecules with two interlocked rings of [6] PAM to show remarkable chiroptical properties.