Fluxionality-Induced Enantiomerisation in Ligand Design

如果一个分子或物质在它的镜像上是不可重叠的，那么它就是手性的。这种性质是控制治疗剂、催化剂和电子设备功能的关键。手性有机分子中最通用和最广泛使用的结构单元是sp3杂化碳中心。一方面，它们的四面体几何形状是制造形状持久的、不可弯曲的结构的理想选择，这些结构以高保真度传输3D立体化学信息。但另一方面，它们缺乏存在于其他立体元件（螺旋、手性平面等）中的能力。在它们的镜像形态之间转换。FIELD通过开拓流动碳中心立体化学弥合了这一知识差距。它开发了刚性小分子的合成，分析和应用，这些小分子在它们的镜像结构之间快速飞行，经历流动性诱导的对映异构化。FIELD建立了获得和利用流动手性碳笼的基本规则。它列举了一系列预计会发生这种类型转化的分子结构，确定了调整动力学，改善对映异构体之间的3D区分以及将笼连接到其他分子组分的方法。重要的是，它开发了将刚性笼的动力学性质传递到立体异构过渡金属离子的方法，拓宽了其应用范围。所得到的刺激响应的fluxionally手性配合物具有的性质，是潜在的有用的放大不对称催化中的对映体诱导，并写入和阅读信息的手性材料。总的来说，FIELD重新思考了有机化学的一个基本方面，形成了矛盾的结构，这些结构同时是刚性的笼子，同时也具有可塑的手性。

A molecule or material is chiral if it is nonsuperimposable on its mirror image. This property is a key handle for controlling the function of therapeutics, catalysts, and electronic devices. The most versatile and widely used structural units in chiral organic molecules are sp3-hybridised carbon centres. On one hand, their tetrahedral geometry is ideal for making shape-persistent, inflexible structures that transmit 3D stereochemical information with high fidelity. But on the other hand, they lack an ability present in other stereogenic elements (helices, chiral planes, etc.) of flipping between their mirror-image forms. FIELD bridges this knowledge gap by pioneering fluxional carbon-centred stereochemistry. It develops the synthesis, analysis, and applications of rigid small molecules that rapidly flit between their mirror-image structures, undergoing fluxionality-induced enantiomerisation. FIELD establishes the ground rules for obtaining and exploiting fluxionally chiral carbon cages. It enumerates a series of molecular structures that are predicted to undergo this type of transformation, identifying ways to tune the dynamics, improve 3D differentiation between enantiomers, and connect the cages to other molecular components. Importantly, it develops ways to transmit the dynamic properties of the rigid cages to stereogenic transition metal ions, broadening the scope for their applications. The resulting stimulus-responsive fluxionally chiral complexes have properties that are potentially useful for amplifying the enantioinduction in asymmetric catalysis, and for writing and reading information with chiroptical materials. Overall, FIELD rethinks a fundamental aspect of organic chemistry by forming paradoxical structures that are simultaneously rigid cages, while also having mouldable chirality.