FLPs and Main Group Catalysis

FLP 和主族催化

• 批准号: RGPIN-2020-04185
• 负责人: Stephan, Douglas
• 金额: $ 7.65万
• 依托单位: University of Toronto
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=739730
• 关键词: FLPs; Main; Group; Catalysis

Chemical industry is the largest consumer of energy worldwide. The most common approach to addressing this problem involves energy-optimize chemical synthesis using catalysis to obtain high value-products from cheap starting materials. Commonly, industrial and academic research chemists use optimized catalytic methodologies aiming for energy efficiency. Indeed, catalysis is central to the manufacture of a myriad of products from pharmaceuticals to agro-chemicals, from polymers to foodstuffs. The vast majority of catalysts in use are based on precious metals, which are expensive, rare, toxic and are obtained with a large carbon footprint. Our research offers a fundamentally new and innovative approach to catalyst design and applications targeting the use of earth-abundant main group compounds. In 2006, we made the transformative discovery of that sterically frustrated Lewis pairs were able to activate H2. This led to FLP catalysts for simple and asymmetric hydrogenations, principally based on electrophilic boron-based FLPs. Moreover, we also showed FLPs could activate a variety of other small molecules, including olefins, alkynes, and the greenhouse gases, CO2, SO2 and N2O. At the same time, we explored and developed Lewis acid catalysis employing a variety of main group cations. Building on our world leading position in main group catalysis, the present research program focuses on advances that target new areas of application. Specifically, we target new, key reactions that are both of broad interest and high impact, Ultimately we hope to transform the notions of catalysis in the chemical community, demonstrating the wide utility of main group species in these efforts. Main group N2 Chemistry: In this proposal, we target a new strategy to capture and convert N2 using earth abundant, non-toxic main-group based compounds. While efforts to make NH3 will be considered direct access to high-value fine chemicals will also be targeted. C-F Bond Activation: We plan to develop strong main group Lewis acidic cation catalysts incorporating P(I), P(III) and P(V) cations, to target reactions of C-F bonds, providing access to libraries of new agrochemicals, drugs and materials derived from known compounds. C-H Bond Activation: In general, almost all strategies to C-H activation utilize directing groups and/or reactive metal catalysts. We plan to exploit the power of FLPs to provide metal-free strategies for catalytic routes to selective C-H derivatization. Main group metathesis: Olefin metathesis is a powerful synthetic tool in organic, polymer and materials chemistry. We have designed cationic P-based species targeting applications in olefin metathesis. In summary, our program targets new main group reagents for important stoichiometric and catalytic reactions. The longer term vision involves the introduction of green, efficient and economically viable main group catalyst technologies to chemical industry.

化学工业是世界上最大的能源消费者。解决这一问题的最常见方法涉及使用催化剂的能量优化化学合成，以从廉价的起始原料中获得高价值的产品。通常，工业和学术研究化学家使用优化的催化方法，旨在提高能源效率。事实上，催化是从药品到农用化学品，从聚合物到食品的无数产品制造的核心。绝大多数使用中的催化剂都是基于贵金属的，贵金属昂贵、稀有、有毒，并且具有很大的碳足迹。我们的研究为催化剂设计和应用提供了一种全新的创新方法，旨在使用地球丰富的主族化合物。在2006年，我们有了一个革命性的发现，空间位阻的刘易斯对能够激活H2。这导致了用于简单和不对称氢化的FLP催化剂，主要基于亲电硼基FLP。此外，我们还表明FLP可以激活各种其他小分子，包括烯烃，炔烃和温室气体，CO2，SO2和N2 O。同时，我们探索和发展了采用多种主族阳离子的刘易斯酸催化。基于我们在主族催化领域的世界领先地位，目前的研究计划侧重于针对新应用领域的进展。具体来说，我们的目标是新的，关键的反应，都是广泛的兴趣和高影响力，最终我们希望改变化学界的催化概念，证明在这些努力中的主要群体物种的广泛用途。 主组N2化学：在这项提案中，我们的目标是一个新的战略，以捕获和转换N2使用地球丰富的，无毒的主族为基础的化合物。虽然努力使氨将被视为直接获得高价值的精细化学品也将有针对性。 C-F键激活：我们计划开发包含P（I）、P（III）和P（V）阳离子的强主族刘易斯酸性阳离子催化剂，以靶向C-F键的反应，提供从已知化合物衍生的新农用化学品、药物和材料的库。 C-H键活化：一般来说，几乎所有的C-H键活化策略都利用导向基团和/或反应性金属催化剂。我们计划利用FLP的力量，为选择性C-H衍生化的催化途径提供无金属策略。烯烃复分解反应是有机、高分子和材料化学中一种强有力的合成工具。我们已经设计了阳离子P-基物质，目标是烯烃复分解中的应用。 总之，我们的计划针对重要的化学计量和催化反应的新的主族试剂。长期愿景包括将绿色、高效和经济上可行的主族催化剂技术引入化学工业。