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

从塑料到药品，80%的化学制品在生产过程中至少需要一个催化步骤。催化，特别是工业上，主要是铂族金属。这些稀缺、高毒性和昂贵的金属极大地限制了可持续发展。它们的优势可以归因于根深蒂固的理解和（氧化还原）机制，通过金属催化剂进行周转，催化剂再生。为了超越（d-嵌段）金属催化，需要新的周转率机制，这些机制必须适应更广泛的元素周期表。该奖学金将开发和展示一种针对p-区块的新的周转机制，并实现使用p-区块元素的可持续催化。该奖学金将使用转硼化催化，这是一种不同于金属催化的氧化还原中性转化。转硼化将利用p-嵌段元素固有的交换反应，并引入控制和选择性，以实现定向催化周转。我们的原理证明结果表明，转硼化催化是可能的，但成功是通过试验和错误实现的。目前还没有明确的认识或指导原则，不对称碳碳键的形成尚未被开发：这是制药和材料开发中最需要的过程。我们将建立跨p-block元素转硼化的基本认识，并建立一套指导原则的开发。这些原理将通过发展两种天生催化的不对称碳-碳键形成反应来证明。我们选择了一个教科书式的化学计量有机硼反应（烯丙基化）和一个没有化学或生物优先权的反应（双还原酯偶联）。最后，我们将把催化作用扩展到硼以外的更宽的p区。该奖学金将打破铂族金属催化的主导地位，巩固化学的可持续未来。

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.