Catalytic methods for the synthesis of main group molecules

主族分子合成的催化方法

• 批准号: RGPIN-2017-04996
• 负责人: Rosenberg, Lisa
• 金额: $ 2.55万
• 依托单位: University of Victoria
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=711330
• 关键词: Catalytic; methods; synthesis; main; group

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.

我们的研究计划致力于通过设计和研究原子经济催化来解决基于硅和磷等无机元素的重要分子和材料合成的可持续性问题。 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，并且可以指导化学反应，当非催化方法产生必须以能源密集型方式分离的混合物时，可以产生单一的理想产品。通过将催化与“原子经济”策略相结合，选择尽可能多的每种试剂分子被掺入所需产物的反应，进一步减少了废物。 重要的含硅和含磷材料（例如具有有用的光学和电子特性的硅基塑料，制药工业需要的P中心分子以使其工艺绿色化）的传统途径依赖于产生大量废物的非催化反应，这些废物主要以消除的卤化物盐（例如NaCl）的形式存在。这是由于使用含有元素-卤素键（例如P-Cl）的试剂，因此我们正在研究含有元素-氢键（例如P-H）的试剂的替代反应。我们的反应要么不产生副产物，要么产生非常小的、轻的副产物，如H2（g）。在某些情况下，这些反应在没有催化剂的情况下根本不会发生，而在其他情况下，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，低能耗），通用的（适用于许多不同类别的试剂分子）和选择性的（导致单一的最理想的产品）。 这个提议借鉴了我在Si-H键催化反应方面的长期经验，专注于催化P-H键活化这一远未开发的领域，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，例如在阻燃剂、农用化学品，特别是药品和香料等精细化学品的合成中。 我们将专注于破译我们设计的催化剂如何与含有P-H键的试剂相互作用以形成新膦分子的细节。然后，我们可以使用这些机械信息来修改我们的催化剂，调整它们以获得最佳性能。 现有的催化剂通过将氢作为H+（质子）除去来活化P-H键。我们将努力改进这些催化剂，使其对单一产品更有效和更有选择性。然而，我们更兴奋的是，探索全新的催化过程的前景，这种催化过程依赖于以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磷催化化学的范式转变。