Long-Lived Fluxional Barbaralyl Cations

长寿命流动 Barbaralyl 阳离子

基本信息

批准号：
EP/N029992/1
负责人：
Paul McGonigal
金额：
$ 12.56万
依托单位：
Durham University
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2016
资助国家：
英国
起止时间：
2016 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FN029992%2F1
关键词：
Long Lived Fluxional Barbaralyl Cations

项目摘要

The covalent bonds that hold atoms together to make molecules are, by and large, flexible linkages that are prone to stretching and bending. This flexibility imparts a degree of responsiveness to molecules' three-dimensional shape that is key in determining their physical properties and mediating their interactions with other molecules. For example, the molecular recognition of a pharmaceutical within the binding site of a protein can induce organisation in one, or even both, of the binding partners. A mutually favourable spatial arrangement (conformation) is stabilised.In certain cases, the structural dynamics of molecules can be extended beyond changes in their conformation to include changes in their constitution (i.e., changes in their atomic skeleton). Processes termed 'dynamic covalent' reactions rely upon chemical transformations that are reversible in nature, allowing specific covalent bonds to be broken and formed freely under the same set of conditions. In this way, molecular fragments come together and break apart over and over again, reversibly forming different compounds of varying shapes and sizes. This research project seeks to explore constitutional dynamics in a rather unique class of compounds. The 'barbaralyl cations' that will be developed are built around a core of nine carbon atoms in a cage-like arrangement. Each carbon atom is connected to two or three similar neighbours. As a result of this particular composition and the type of covalent bonds that make up the core, the carbon atoms are able to reversibly trade bonds with one another, switching positions with their neighbours. As one bond breaks, another is made and the outcome is that the barbaralyl cation core is 'fluxional'. When different groups are appended to this fluxional core, the molecule as a whole develops the property of being able to change its shape dramatically, not just in terms of its conformation, but also in terms of its constitution. It becomes a 'shapeshifting molecule'. Unlike the vast majority of dynamic covalent processes, this rearrangement occurs entirely within single molecules, meaning that the rate at which it occurs is not dependent on the presence of other reactants and their concentration. The linkages at the centre of the molecule interchange, causing the positions and orientations of the functional groups around the exterior to be switched and giving rise to hundreds (or even thousands!) of different structural permutations.Importantly, the shapeshifting molecules developed during this research will not require onerous preparation, but rather they will be made using relatively straightforward methods, overcoming one of the major impediments associated with the handful of related shapeshifting molecules that have been studied in the past. Ultimately, constitutional dynamics of this kind, occurring within a single molecule, will offer a new means through which to search for structures with mutually stabilising binding interactions with conceivably any target of interest. Applications, therefore, may lie in the improved design of molecular components for sensing medicinally relevant species.

将原子固定在一起以使分子的共价键在很大程度上易于伸展和弯曲。这种柔韧性赋予了对分子的三维形状的一定程度的响应，这是确定其物理特性并介导其与其他分子相互作用的关键。例如，在蛋白质的结合位点内对药物的分子识别可以在结合伴侣中诱导组织，甚至可以诱导组织。稳定了互惠互利的空间排列（构象）。在某些情况下，分子的结构动力学可以扩展到其构象的变化之外，以包括其构成的变化（即，其原子骨架的变化）。称为“动态共价”反应的过程依赖于本质上可逆的化学转化，从而使特定的共价键在相同的条件下被打破并自由形成。这样，分子碎片聚集在一起，一遍又一遍地分解，可逆地形成不同形状和尺寸的不同化合物。该研究项目旨在探索相当独特的化合物中的宪法动态。将要开发的“野丙酰基阳离子”建立在笼子状的九个碳原子的核心周围。每个碳原子都连接到两个或三个相似的邻居。由于这种特殊的组成和构成核心的共价键的类型，碳原子能够彼此可逆地交易债券，从而与邻居切换位置。随着一个键断裂，产生了另一个键，结果是野丙酰阳离子核是“倒数的”。当将不同的群体附加到该磁通核心上时，整个分子都会发展出能够巨大改变其形状的特性，不仅是其构象，而且在其构成方面。它变成了“变形分子”。与绝大多数动态共价过程不同，该重排完全发生在单分子内，这意味着它发生的速率并不取决于其他反应物的存在及其浓度。分子互换中心的链接，导致外部官能团的位置和方向可以切换并产生数百个不同结构排列的数百个（甚至数千个！），这是临时的。在这项研究中，造型分子在这项研究过程中不需要繁重的准备，而是使用相关的稳定的准备，而是相关的，相关的是相关的，超出了相关的范围，而不是相关的，而不是相互的，而不是相互的，而是超级构成的方法，那么多地位的方法是一定的。过去研究的变形分子。最终，这种发生在单个分子中的这种宪法动力学将提供一种新的手段，通过该方法可以通过可以搜索与可以想象的任何感兴趣的目标相互稳定结合相互作用的结构。因此，应用可能在于改善分子成分的设计，以感知药物相关物种。