Catalytic methods for the synthesis of main group molecules

我们的研究计划致力于通过原子经济催化的设计和研究，解决以硅和磷等无机元素为基础的重要分子和材料合成中的可持续性问题。*催化是开发可持续制造工艺的最终工具，因为它减少了制造新分子和材料所需的能量，并且当非催化方法得到混合物时，它可以引导化学反应得到单一的、理想的产品，然后必须以能量密集型的方式分离这些混合物。通过将催化与“原子经济”策略相结合，进一步减少废物，选择尽可能多地将每个试剂分子结合到所需产品中的反应。*重要的含硅和含磷材料(例如，具有有用的光学和电子性能的硅基塑料，制药工业需要的P中心分子)依赖于产生大量废物的非催化反应，主要是以消除的卤化物盐(例如，氯化钠)的形式。这是由于使用了含有元素-卤键的试剂(例如P-Cl)，所以我们正在寻找含有元素-氢键的试剂的替代反应(例如P-H)。我们的反应不会产生副产品，也不会产生像H2(G)这样的非常小的、轻的副产品。在某些情况下，没有催化剂，这些反应根本不会发生，而在另一些情况下，催化剂有助于反应更快地发生。我们努力确保这些反应是高效的(快速、低能量)、通用的(适用于许多不同类别的试剂分子)和选择性的(产生单一最理想的产品)。*这项建议借鉴了我在硅-氢键催化反应方面的长期经验，将重点放在远不发达的催化P-H键活化领域，我们已经成为该领域的积极参与者。我们正在制造的“膦”分子本身就是重要的试剂，例如在合成阻燃剂、农用化学品，特别是精细化学品(如药品和香水)的合成中。*我们将专注于破译我们设计的催化剂如何与含有P-H键的试剂相互作用的秘密细节，以允许新的膦分子形成。然后，我们可以使用这些机械信息来修改我们的催化剂，调整它们以实现最佳性能。*现有的催化剂通过以H+(质子)的形式去除氢来激活P-H键。我们将致力于改进这些催化剂，使其对单一产品更有效率和选择性。然而，我们更兴奋的是，探索全新的催化过程的前景，这些过程依赖于以H(氢化物)或H(氢原子)的形式去除氢。这些新项目的成功将代表着磷催化化学的范式转变。

Our research program works to address issues of sustainability in the synthesis of important molecules and materials based on inorganic elements such as silicon and phosphorus, through the design and study of atom economic catalysis.***Catalysis is the ultimate tool in developing sustainable manufacturing processes, since it reduces the energy required to make new molecules and materials, and can direct chemical reactions to give a single, desirable product when non-catalytic methods give mixtures that must then be separated in energy-intensive ways. Waste is even further reduced through the coupling of catalysis with the strategy of “atom economy”, choosing reactions where as much as possible of each reagent molecule is incorporated into the desired product.***Traditional routes to important silicon- and phosphorus-containing materials (e.g. Si-based plastics with useful optical and electronic properties, P-centered molecules needed by the pharmaceutical industry to green up their processes) rely on non-catalytic reactions that generate huge amounts of waste, mostly in the form of eliminated halide salts (e.g. NaCl). This results from using reagents containing element-halogen bonds (e.g. P-Cl), so we are looking at alternative reactions of reagents containing element-hydrogen bonds (e.g. P-H). Our reactions generate either no byproducts or very small, light ones like H2(g). In some cases, these reactions won't happen at all without catalysts, while in other cases the catalysts help the reactions occur faster. We strive to ensure these reactions are efficient (fast, low energy), general (work for many different classes of reagent molecules), and selective (lead to the single most desirable product). ***This proposal draws on my long experience in the catalytic reactions of Si-H bonds to focus on the far less-developed area of catalytic P-H bond activation, in which we have become active participants. The “phosphine” molecules we're making are important reagents in their own right, e.g. in the synthesis of fire retardants, agrochemicals, and especially fine chemicals like pharmaceuticals and fragrances. ***We will concentrate on deciphering the intimate details of how the catalysts we design interact with reagents containing P-H bonds to allow the new phosphine molecules to form. We can then use this mechanistic information to modify our catalysts, tuning them for optimal performance. ***Existing catalysts activate the P-H bond by removing the hydrogen as H+ (proton). We'll work on improving these catalysts to make them more efficient and selective for single products. We are even more excited, though, by the prospect of exploring entirely new catalytic processes that rely on removing the hydrogen as either H (hydride) or H (hydrogen atom). The success of these new ventures will represent a paradigm shift in the catalytic chemistry of phosphorus.