The Generation of Enantioenriched Radicals Under HAT Photocatalysis: a C2-Desymmetrisation Approach

HAT 光催化下生成对映体富集的自由基：C2 去对称化方法

• 批准号: 2751504
• 金额: --
• 依托单位: University of Cambridge
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2751504
• 关键词: Generation; Enantioenriched; Radicals; Under; HAT

Enantioenriched molecules are commonplace within academic research and in a wide range of industries; C2-symmetric diols and their derivatives are an important sub-class found within pharmaceuticals and beyond. The proposed research intends to merge HAT catalysis and asymmetric catalysis to enantioselectivity generate a-hydroxy radicals from prochiral C2-symmetric diols to access a wide range of enantioselective C-H bond functionalisations with important synthetic results, with the potential expansion to other C2-symmetric substrates. This will establish a new, green approach to enantioselective HAT catalysis unseen in the literature.The research plan primarily entails modification of MacMillan's tricatalytic HAT system, where the photocatalytic Giese addition of alcohols was observed under TBAP catalysis, through use of chiral phosphoric acids. Detailed exploration of alternative photocatalysts and HAT catalysts shall be conducted, alongside miscellaneous approaches. The opportunity for intra-CDT collaboration to benefit optimisation, mechanistic understanding, substrate scope and scale up shall be explored once a reasonable system is found.

对映体富集分子在学术研究和广泛的行业中很常见； C2-对称二醇及其衍生物是药物及其他领域的一个重要子类。拟议的研究旨在将 HAT 催化和不对称催化合并，以对映选择性从前手性 C2 对称二醇生成 α-羟基自由基，以获得广泛的对映选择性 C-H 键功能化，并获得重要的合成结果，并有可能扩展到其他 C2 对称底物。这将建立一种新的、绿色的对映选择性 HAT 催化方法，这是文献中未曾见过的。该研究计划主要需要修改 MacMillan 的三催化 HAT 系统，其中通过使用手性磷酸，在 TBAP 催化下观察到醇的光催化 Giese 加成。应与其他方法一起对替代光催化剂和 HAT 催化剂进行详细探索。一旦找到合理的系统，就应探索 CDT 内部合作的机会，以实现效益优化、机制理解、底物范围和扩大规模。