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式，这使我们能够在催化剂中应用和利用这种行为，以构建合成有价值的功能。目标转换包括C-C，C-N和C-O键形成，这些形成具有用于构建增值产品的潜力，例如香水，农业化学和药物。由于催化剂结构的独特金属配体反应性，特定类型的键结构将与现有方法不同。我们的研究以三种不同的金属配体反应性模式：1。结构响应的配体，以促进键形成和替代反应。我们已经开发了一种结构响应的配体，我们的目的是确定配体动力学促进有机金属反应并阐明如何控制这些作用。示例反应将是CSP3-CSP3耦合和取代，这是许多催化反应的重要步骤，因此具有对催化的广泛影响。 2。布朗斯特基体配体用Ni（II）促进有氧氧化催化的C-H激活。 C-C耦合催化已通过PD（II）与分子内Bronsted碱一起通过PD（II）激活氧化还原中性CSP2-H激活进行了革命。我们旨在以Ni（II）和氢氧化物作为基础探索CSP3-H激活。成功的反应只会给出水作为无害的副产品，并且该反应与Ni（II）促进的烯丙基氧化与O2兼容。这些反应在一起将带来前所未有的，有选择性的，一步，无添加剂的有氧氧化C-H键的镍。 3。质子转移配体，以促进无添加剂间分子氢化。许多催化反应包括质子转移（PT）步骤，例如C-C或C-E键形成。配体上的内部碱不取消添加剂的内部基础，而不是分子间碱基的基础，而不是对添加剂的需求，并且可以加速反应速率。我们的目标是运用PT配体的经验，以开发RU和FE催化剂，以形成C-N键形成，以提供合成的亚胺和魔金蛋白产品。