Catalytic Stereoretentive-Enantioconvergent Cross-Coupling Reactions

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This project will experimentally establish a new concept in asymmetric synthesis: stereoretentive-enantioconvergentcatalysis. This will represent a completely new method for accessing enantiopure materials starting from racemicsubstrates and will therefore impact all areas of synthetic chemistry. The ability to synthesise chiral molecules inenantiopure form is vitally important, most recognisably for the pharmaceutical industry. This is because the molecules oflife are chiral (e.g., D-sugars and L-amino acids) and enantiomers often interact very differently with living organisms.Classically, asymmetric synthesis utilising racemic substrates is limited to achieving a maximum yield of 50% (e.g., kineticresolutions). Enantioconvergent catalysis avoids this limitation with both enantiomers of the starting material beingconverted into a single enantioenriched product, thanks to complex stereoablative or stereomutative de-racemisationprocesses. This project will establish a conceptually new stereoretentive-dimerisation approach that results in bothenantiomers of the starting material being incorporated into the product with no de-racemisation required. This new conceptwill prove highly valuable for the synthesis of small enantiopure building blocks, which will be of high value in many areas ofsynthesis, and also for more complex late-stage transformations in complex molecule synthesis. Several approaches willbe pursued to demonstrate proof-of-principle, and applications in the synthesis of complex natural and unnatural productswill then be used to demonstrate the potential of stereoretentive-enantioconvergent catalysis in target-orientated synthesis.