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.

轴向手性是一个用语，用于指代由手性轴周围成对的四个组的非平面布置产生的立体异构主义。这种化合物用阻碍的双毛，某些类别的螺纹蛋白化合物和艾伦来体现。促分散性是一种现象，通过限制单个键的旋转会导致立体异构体的形成，并且是天然产物，药物分子和催化剂的关键特征。在所有这些领域中，它的重要性越来越重要，这意味着，抗体异构化合物的对映选择性合成的新方法非常重要。该建议的目的是开发和利用用于轴向手性分子的新催化对映选择性方法。我们建议可以通过动力学分辨率和动态动力学分辨过程来使用手性铵反离子来控制这些反应的立体化学。我们还提出了一个光介导的种族化过程，该过程可以与反离子介导的动力学分辨率结合起来，从而使双子体的动态动力学分辨率具有较大的障碍物在室温下旋转。最后，我们旨在将这些反应用作示例，以探测对映体相位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