FLPs and Main Group Catalysis

化学工业是世界上最大的能源消耗行业。解决这一问题的最常见方法是使用催化进行能量优化的化学合成，以从廉价的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旨在提高能源效率的优化催化方法。事实上，从药品到农用化学品，从聚合物到食品，各种产品的生产都离不开催化作用。目前使用的绝大多数催化剂都是以贵金属为基础的，贵金属价格昂贵，稀有，有毒，而且获得时需要大量的碳足迹。我们的研究为以富含稀土的主族化合物为目标的催化剂设计和应用提供了一种全新的创新方法。2006年，我们取得了革命性的发现，空间受挫的Lewis对能够激活H2。这导致了用于简单和不对称加氢的FLP催化剂，主要基于亲电的硼基FLP。此外，我们还表明，氟氯烃类化合物还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，探索开发了利用多种主要基团阳离子的Lewis酸催化剂。在我们主要基团催化领域世界领先地位的基础上，目前的研究计划专注于针对新应用领域的进展。具体地说，我们的目标是具有广泛兴趣和高影响的新的关键反应，最终我们希望改变化学社区中催化的概念，展示主要基团物种在这些努力中的广泛用途。主族氮气化学：在这项建议中，我们的目标是使用地球上丰富的、无毒的主族化合物来捕获和转化氮气的新策略。虽然制造NH3的努力将被视为直接获得高价值精细化学品的目标，但也将成为目标。C-F键活化：我们计划开发包含P(I)、P(III)和P(V)阳离子的强主基Lewis酸性阳离子催化剂，以靶向C-F键的反应，提供访问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活化策略都使用直接基团和/或活性金属催化剂。我们计划利用Flp的力量，为选择性C-H衍生化提供无金属的催化路线。主基团复分解：烯烃复分解是有机、聚合物和材料化学中强有力的合成工具。我们设计了阳离子磷基物种在烯烃歧化反应中的靶向应用。总而言之，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。较长期的愿景包括将绿色、高效和经济可行的主族催化剂技术引入化学工业。

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.