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: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748368
• 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.

化学工业是全球最大的能源消费者。解决此问题的最常见方法是使用催化从廉价的起始材料中获得高价值产生的能量优化化学合成。通常，工业和学术研究化学家使用旨在能源效率的优化催化方法。的确，催化是从药物到农业化学物质（从聚合物到食物的农业化学物质）生产的核心。使用的绝大多数催化剂都是基于贵金属，这些金属昂贵，稀有，有毒，并以大碳足迹获得。我们的研究提供了一种从根本上进行新的和创新的方法，用于催化剂设计和应用，以使用地球丰富的主要群体化合物。在2006年，我们对刘易斯沮丧的刘易斯对的变革性发现能够激活H2。这导致了FLP催化剂的简单和不对称氢化，主要基于亲电硼的FLP。此外，我们还显示FLP可以激活其他各种小分子，包括烯烃，炔烃和温室气体，CO2，SO2和N2O。同时，我们采用了各种主体阳离子探索并开发了路易斯酸催化。在我们世界主要催化中领先地位的基础上，本研究计划的重点是针对新的应用领域的进步。具体而言，我们针对既有广泛兴趣又高影响力的新的主要反应，最终我们希望改变化学界催化的观念，并在这些努力中证明了主要群体的广泛效用。 主要组N2化学：在此提案中，我们针对一种新的策略，使用大量的，无毒的主要基团化合物捕获N2。尽管制造NH3的努力将被视为直接进入高价值精美化学品。 C-F键激活：我们计划开发结合P（I），P（III）和P（V）阳离子的强大主要组Lewis酸性阳离子催化剂，以靶向C-F键的反应，从而访问来自已知化合物的新农业化学，药物和材料的库。 C-H键激活：通常，C-H激活的几乎所有策略都使用指导组和/或反应性金属催化剂。我们计划利用FLP的功率为选择性C-H衍生化的催化路线提供无金属的策略。主要组复合：烯烃的元解关系是有机，聚合物和材料化学的强大合成工具。我们已经设计了基于阳离子P的物种靶向烯烃化合物中的应用。 总而言之，我们的程序针对重要的化学计量和催化反应的新主要组试剂。长期的视力涉及将绿色，高效且经济上可行的主要群催化剂技术引入化学工业。