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

富含对映体的分子在学术研究和广泛的工业中是很常见的；C2对称的二醇及其衍生物是在制药和其他领域中发现的一个重要的子类。这项研究旨在将HAT催化和不对称催化相结合，以从前手性C2对称二醇生成不对称的α-羟基自由基，从而获得广泛的不对称C-H键功能化，具有重要的合成结果，并有可能扩展到其他C2对称底物。这将建立一种新的、绿色的方法来实现对映体选择性HAT催化。研究计划主要包括对MacMillan的三催化HAT体系进行修饰，其中通过使用手性磷酸，在TBAP催化下观察到醇的光催化Giese加成反应。除其他办法外，还应对替代光催化剂和HAT催化剂进行详细探索。一旦找到一个合理的系统，就应探索CDT内部协作的机会，以利于优化、机械理解、基材范围和规模扩大。

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.