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

对映体富集的分子在学术研究和广泛的工业中是常见的; C2-对称二醇及其衍生物是在制药和其他领域中发现的重要子类。该研究旨在将HAT催化和不对称催化相结合，从前手性C2-对称二醇中对映选择性地产生α-羟基自由基，以获得广泛的对映选择性C-H键官能化，并获得重要的合成结果，并可能扩展到其他C2-对称底物。这将建立一个新的，绿色的方法，对映选择性HAT催化unseen在literary.The研究计划主要涉及修改MacMillan的tricatalytic HAT系统，在TBAP催化下，通过使用手性磷酸观察到的醇的光催化Giese加成。应对替代光催化剂和HAT催化剂以及其他方法进行详细研究。一旦找到合理的系统，应探索CDT内部协作的机会，以利于优化、机械理解、底物范围和规模扩大。

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.