Fluxionality-Induced Enantiomerisation in Ligand Design

配体设计中的流动性诱导的对映异构化

• 批准号: EP/Z00036X/1
• 负责人: Paul McGonigal
• 金额: $ 221.73万
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2024
• 资助国家: 英国
• 起止时间: 2024 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FZ00036X%2F1
• 关键词: Fluxionality; Induced; Enantiomerisation; Ligand; Design

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.

如果分子或材料在镜像上不受欢迎，则是手性的。该特性是控制治疗剂，催化剂和电子设备功能的关键手柄。手性有机分子中用途最广泛，最广泛使用的结构单元是SP3杂交碳中心。一方面，它们的四面体几何形状非常适合形成形状敏感的，僵化的结构，该结构以高忠诚传输3D立体化学信息。但是，另一方面，它们缺乏在其他立体元素（螺旋，手性平面等）之间翻转其镜像形式之间的能力。田间通过开创以碳为中心的立体化学来弥合这一知识差距。它发展了刚性小分子的综合，分析和应用，这些分子在其镜像结构之间迅速飞行，从而经历了逆转性诱导的对映异构化。田地建立了获得和利用倒数手性碳笼的基本规则。它列举了一系列分子结构，这些结构预测会经历这种类型的转换，确定调整动力学的方法，改善对映异构体之间的3D差异，并将笼子连接到其他分子成分。重要的是，它开发了将刚性笼的动态特性传递到立体过渡金属离子，从而扩大其应用范围的方法。所得的刺激反应性磁通性手性复合物具有潜在的特性，可用于扩增不对称催化的对映体诱导，以及使用手学材料的写作和阅读信息。总体而言，田野通过形成同时具有刚性笼子的矛盾结构，同时具有可行的手性，从而重新考虑了有机化学的基本方面。