Counter-ion Directed Enantioselective Approaches to Axially Chiral Materials

反离子定向对映选择性方法制备轴向手性材料

• 批准号: EP/R005826/1
• 负责人: Martin Smith
• 金额: $ 87.65万
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FR005826%2F1
• 关键词: Counter; ion; Directed; Enantioselective; Approaches

Axial chirality is a term used to refer to stereoisomerism resulting from the non-planar arrangement of four groups in pairs around a chirality axis. Such compounds are exemplified by hindered biaryls, certain classes of spiro compounds, and allenes. Atropisomerism is a phenomenon whereby restricted rotation about a single bond leads to the formation of stereoisomers, and is a key feature of natural products, drug molecules and catalysts. It's increasing importance in all of these fields means that new methods for the enantioselective synthesis of atropisomeric compounds are extremely important. The aim of this proposal is to develop and exploit new catalytic enantioselective methods for the construction of axially chiral molecules. We propose that chiral ammonium counter-ions can be employed to control the stereochemistry of these reactions through kinetic resolution and dynamic kinetic resolution processes. We also propose a light-mediated racemization process that can be coupled with a counter-ion-mediated kinetic resolution, enabling the dynamic kinetic resolution of biaryls with large barriers to rotation at room temperature. Finally, we aim to use these reactions as exemplars to probe the kinetics and mechanism of enantioselective phase-transfer catalysis.

轴向手性是用于指由四个基团围绕手性轴成对的非平面排列产生的立体异构的术语。这类化合物的例子有受阻联芳基、某些类别的螺环化合物和联烯。阻转异构现象是一种围绕单键的受限旋转导致形成立体异构体的现象，并且是天然产物、药物分子和催化剂的关键特征。由于阻转异构体在这些领域的重要性日益增加，因此，对映选择性合成阻转异构体化合物的新方法显得尤为重要。本研究的目的是开发和利用新的催化对映选择性方法来构建轴向手性分子。我们建议手性铵抗衡离子可以用来控制这些反应的立体化学通过动力学拆分和动态动力学拆分过程。我们还提出了一个光介导的外消旋过程，可以加上一个反离子介导的动力学决议，使动态动力学决议的联芳化合物在室温下旋转的大障碍。最后，我们的目标是以这些反应为例，探讨不对称相转移催化的动力学和机制。

项目成果

Visible-Light-Mediated Heterocycle Functionalization via Geometrically Interrupted [2+2] Cycloaddition

通过几何中断的可见光介导的杂环官能化 [2 2] 环加成

• DOI: 10.1002/ange.202009704
• 发表时间: 2020
• 期刊: Angewandte Chemie
• 作者: Popescu M

Visible-Light-Mediated Heterocycle Functionalization via Geometrically Interrupted [2+2] Cycloaddition.

• DOI: 10.1002/anie.202009704
• 发表时间: 2020-12-14
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Popescu MV;Mekereeya A;Alegre-Requena JV;Paton RS;Smith MD
• 通讯作者: Smith MD

Interrogating the configurational stability of atropisomers

探讨阻转异构体的构型稳定性

• DOI: 10.1038/s41596-023-00859-y
• 发表时间: 2023
• 期刊: Nature Protocols
• 影响因子: 14.8
• 作者: Heeb J