FLPs and Main Group Catalysis

化学工业是世界上最大的能源消耗者。解决这一问题的最常见方法是利用催化剂进行能源优化的化学合成，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优化的催化方法，旨在提高能源效率。事实上，从药品到农用化学品，从聚合物到食品，催化作用是制造无数产品的核心。目前使用的绝大多数催化剂都是基于贵金属的，这些贵金属价格昂贵、稀有、有毒，而且碳足迹很大。我们的研究为催化剂的设计和应用提供了一种全新的创新方法，目标是利用地球上丰富的主基化合物。2006年，我们有了革命性的发现，即空间受挫的路易斯对能够激活H2。这导致了简单和不对称氢化的FLP催化剂，主要基于亲电性硼基FLP。此外，我们还发现FLPs可以激活多种其他小分子，包括烯烃、炔烃以及温室气体CO2、SO2和N2O。同时，探索和发展了多种主基阳离子的路易斯酸催化反应。基于我们在主基团催化方面的世界领先地位，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，既广泛的兴趣和高影响，最终我们希望改变催化在化学社区的概念，证明在这些努力中的主要类群物种的广泛效用。主基团N2化学：在本提案中，我们的目标是利用地球上丰富的无毒主基团化合物捕获和转化N2的新策略。虽然NH3的生产将被视为直接获得高价值精细化学品的努力也将成为目标。C-F键活化：我们计划开发包含P(I)， P（III）和P(V)阳离子的强主基团Lewis酸性阳离子催化剂，以靶C-F键的反应，为新的农用化学品，药物和已知化合物衍生的材料提供访问库。C-H键活化：一般来说，几乎所有的C-H活化策略都利用导向基团和/或活性金属催化剂。我们计划利用FLPs的力量，为选择性碳氢化合物衍生化的催化途径提供无金属策略。主要基团分解法：烯烃分解法是有机化学、高分子化学和材料化学中强有力的合成手段。我们设计了基于阳离子p基的物种靶向在烯烃复分解中的应用。总之，我们的计划目标是新的主基团试剂用于重要的化学计量和催化反应。长期目标是将绿色、高效、经济可行的主要催化剂技术引入化工行业。

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.