TTS APC: Transborylation: A Turnover Strategy for Asymmetric p-Block Catalysis

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80% of manufactured chemicals, from plastics to pharmaceuticals, require at least one catalysed-step in their production. Catalysis,particularly industrially, is dominated by the platinum-group metals. These scarce, high toxicity and expensive metals significantly limit sustainably. Their dominance can be attributed to the entrenched understanding and (redox) mechanisms by which metal catalysts undergo turnover, catalyst regeneration. To move beyond (d-block) metal catalysis, new turnover mechanisms are needed and these must be tailored to the wider periodic table. This Fellowship will develop and demonstrate a new turnover mechanism tailored to the p-block and enable sustainable catalysis using p-block elements to be realised.This Fellowship will enable catalysis using transborylation, a redox neutral turnover distinct from metal catalysis. Transborylation will exploit the inherent exchange reactions of p-block elements and introduce control and selectivity to enable directed catalytic turnover. Out proof of principle results have shown transborylation catalysis is possible, but success has been achieved through trial and error. No clear understanding or guiding principles have been established and asymmetric carbon-carbon bond formation is yet to be exploited: the process most required in pharmaceutical and materials development.We will build a fundamental understanding of transborylation across p-block elements and establish a set of guiding principals for exploitation. These principles will then be demonstrated by developing two born-catalysed asymmetric carbon-carbon bond forming reactions. We have chosen a textbook, stoichiometric organoboron reaction (allylation) and a reaction without chemical or biological precedence (doubly reductive ester coupling). Finally we will extend catalysis beyond boron species to the wider p-block. This Fellowship will break the dominance of platinum-group metal catalysis and underpin the sustainable future of chemistry.