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

TTS APC：硼基转移：不对称 p 嵌段催化的周转策略

• 批准号: EP/Y029321/1
• 负责人: Stephen Thomas
• 金额: $ 23.84万
• 依托单位: University of Edinburgh
• 依托单位国家: 英国
• 项目类别: Fellowship
• 财政年份: 2024
• 资助国家: 英国
• 起止时间: 2024 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FY029321%2F1
• 关键词: TTS; APC; Transborylation; Turnover; Strategy

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.

从塑料到药品，80% 的化学品在其生产过程中至少需要一个催化步骤。催化作用，尤其是工业催化作用，以铂族金属为主。这些稀有、高毒性和昂贵的金属严重限制了可持续发展。它们的主导地位可归因于对金属催化剂进行周转和催化剂再生的根深蒂固的理解和（氧化还原）机制。为了超越（d-区）金属催化，需要新的周转机制，并且这些机制必须适应更广泛的元素周期表。该奖学金将开发并展示一种针对 p 嵌段量身定制的新周转机制，并利用 p 嵌段元素实现可持续催化。该奖学金将使用硼基转移（一种不同于金属催化的氧化还原中性周转）进行催化。硼基转移将利用 p 区元素的固有交换反应，并引入控制和选择性以实现定向催化转换。原理证明结果表明转硼基化催化是可能的，但成功是通过反复试验取得的。尚未建立明确的理解或指导原则，不对称碳-碳键的形成尚未得到开发：这是制药和材料开发中最需要的过程。我们将建立对跨 p 区元素的硼基转移的基本理解，并建立一套开发的指导原则。然后，将通过开发两种自然催化的不对称碳-碳键形成反应来证明这些原理。我们选择了教科书，化学计量有机硼反应（烯丙基化）和没有化学或生物优先的反应（双还原酯偶联）。最后，我们将催化作用从硼物质扩展到更广泛的 p 区。该奖学金将打破铂族金属催化的主导地位，并支撑化学的可持续未来。