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

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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.