Structurally- and Proton-Responsive Ligands for Sustainable Catalysis

用于可持续催化的结构和质子响应配体

• 批准号: RGPIN-2020-06147
• 负责人: Blacquiere, Johanna
• 金额: $ 3.5万
• 依托单位: University of Western Ontario
• 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=747783
• 关键词: Structurally; Proton; Responsive; Ligands; Sustainable

We explore new paradigms in metal ligand reactivity, which allows us to apply and exploit this behaviour in catalysts for the construction of synthetically valuable functionalities. Target transformations include C-C, C-N and C-O bond formations that have the potential to be used in the construction of value-added products such as fragrances, agrochemicals and pharmaceuticals. The specific types of bond constructions will be distinct from existing methods due to the unique metal-ligand reactivity of the catalyst structures. Our research targets three distinct modes of metal-ligand reactivity: 1. Structurally-Responsive Ligands to Promote Bond Formation and Substitution Reactions. We have developed a structurally-responsive ligand and we aim to establish that the ligand dynamics promote organometallic reactions and to elucidate how to control these actions. The exemplar reactions will be Csp3-Csp3 coupling and substitution, which are essential steps in many catalytic reactions and thus have the potential for broad impact to catalysis. 2. Bronsted-Basic Ligands to Promote C-H Activation with Ni(II) for Aerobic Oxidation Catalysis. C-C coupling catalysis has been revolutionized by redox neutral Csp2-H activation by Pd(II) in concert with an intramolecular Bronsted base. We aim to explore Csp3-H activation with Ni(II) and hydroxide as the base. A successful reaction would give only water as an innocuous by-product and the reaction would be compatible with Ni(II) promoted allylic oxidation with O2. Together these reactions would give the unprecedented, selective, one-step, additive-free aerobic oxidation of C-H bonds by nickel. 3. Proton-Transfer Ligands to Promote Additive-Free Intermolecular Hydroamination. Many catalytic reactions include proton-transfer (PT) steps en route to, for example, C-C or C-E bond formation. Instead of an intermolecular base to mediate PT, an internal base on the ligand eliminates the need for additives and can accelerate reaction rates. We aim to apply our experience with PT ligands to develop Ru and Fe catalysts for selective C-N bond formation to give synthetically versatile imine and enamine products.

我们探索金属配体反应性的新范例，这使我们能够在催化剂中应用和利用这种行为来构建有价值的功能。目标转化包括C-C、C-N和C-O键的形成，这些键有可能用于构建增值产品，如香料、农用化学品和药品。由于催化剂结构的独特金属-配体反应性，键结构的具体类型将不同于现有方法。我们的研究针对三种不同的金属配体反应模式：1。促进键形成和取代反应的结构响应配体。我们已经开发了一种结构响应配体，我们的目标是建立，配体动力学促进有机金属反应，并阐明如何控制这些行动。典型的反应将是Csp 3-Csp 3偶联和取代，这是许多催化反应中的重要步骤，因此对催化具有广泛的影响。 2. Bronsted碱性配体促进Ni（II）催化C-H活化用于有氧氧化催化。C-C偶联催化已经通过Pd（II）与分子内布朗斯台德碱协同作用的氧化还原中性Csp 2-H活化而发生了革命性的变化。我们的目的是探索Csp 3-H活化与Ni（II）和氢氧化物作为碱。一个成功的反应将只得到水作为一个无害的副产物，该反应将是相容的Ni（II）促进烯丙基氧化与O2。这些反应结合在一起，将产生前所未有的、选择性的、一步的、无添加剂的镍对C-H键的有氧氧化。3.质子转移配体促进无添加剂的分子间氢胺化。许多催化反应包括质子转移（PT）步骤，例如形成C-C或C-E键。取代介导PT的分子间碱，配体上的内部碱消除了对添加剂的需要，并且可以加速反应速率。我们的目标是应用我们在PT配体方面的经验来开发Ru和Fe催化剂，用于选择性地形成C-N键，以合成多用途的亚胺和烯胺产品。