New strategy for ruthenium olefin metathesis catalysts using dianionic tridentate ligands

使用双阴离子三齿配体的钌烯烃复分解催化剂的新策略

• 批准号: RGPIN-2016-05314
• 负责人: Lavoie, Gino
• 金额: $ 1.82万
• 依托单位: York University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=615621
• 关键词: New; strategy; ruthenium; olefin; metathesis

Olefin metathesis has become a formidable tool for synthetic chemists to create carbon-carbon double bonds. This transformation, made possible by the use of metal carbene catalysts, has had a remarkable influence of the development of new materials (polymers/plastics) and organic compounds, including those with biological activity (drugs). The importance of this reaction is reflected in the 2005 Nobel Prize in Chemistry awarded to Chauvin, Schrock and Grubbs. Although remarkable progress has been made in the past decades, the thermal stability of ruthenium-based catalysts and their ability to achieve good selectivity for a wide range of reactants (also known as substrates) and transformations still remain an issue. For instance, poor thermal stability results in decomposition of these catalysts over the course of the reaction with a decrease in productivity. Furthermore, poor selectivity of the catalyst leads to mixtures of products that can be difficult to isolate in their pure form. This is especially concerning for biologically-active compounds where side-product contaminants can cause severe undesired side effects. A strategy to develop new catalysts capable of mediating olefin metathesis is presented in the proposal. The approach leverages observations made by the Lavoie group and by others in the field. Catalysts with building blocks that can easily be modified are proposed and used to modulate the performance of these catalysts in olefin metathesis. The initial focus of the research is aimed at producing thermally robust catalysts that can be used in several types of olefin metathesis transformations with a wide range of substrates. Studying the effects of the building blocks on the catalysts will give us fundamental knowledge to further enhance their performance through structure-activity relationships. In addition to research done in conventional synthetic laboratories, new advances in computational chemistry will be incorporated in the research program to gain further insight into the catalysis. The development of catalyst systems with excellent thermal stability, activity, and substrate scope will greatly benefit from this multi-prong approach. The chemical structure of these new systems will be further tailored at a later stage (5 to 10-year timeframe) to address other complex issues, including that of selectivity. In the long term, this research program will lead to easy and controlled ways to make carbon-carbon double bonds, giving access to materials and organic compounds with new and enhanced properties, including drugs with potent biological activity.

烯烃复分解已经成为合成化学家创造碳碳双键的强大工具。通过使用金属卡宾催化剂而实现的这种转化对新材料（聚合物/塑料）和有机化合物（包括具有生物活性的化合物（药物））的开发产生了显着的影响。这个反应的重要性反映在2005年诺贝尔化学奖授予Chauvin，Schrock和Grubbs。虽然在过去几十年中已经取得了显着的进展，但基于铼的催化剂的热稳定性及其对广泛的反应物（也称为底物）和转化实现良好选择性的能力仍然是一个问题。例如，差的热稳定性导致这些催化剂在反应过程中分解，生产率降低。此外，催化剂的选择性差导致产物的混合物可能难以以其纯形式分离。这对于副产物污染物可能导致严重的不期望的副作用的生物活性化合物尤其重要。 提出了开发新型烯烃复分解催化剂的策略。该方法利用了Lavoie小组和该领域其他人的观察结果。提出了具有可以容易地改性的结构单元的催化剂，并用于调节这些催化剂在烯烃复分解中的性能。该研究的最初重点是生产热稳定的催化剂，可用于多种类型的烯烃复分解转化，具有广泛的底物。研究结构单元对催化剂的影响将为我们提供基础知识，以通过结构-活性关系进一步提高其性能。除了在传统的合成实验室进行的研究外，计算化学的新进展将被纳入研究计划，以进一步了解催化作用。 具有优异的热稳定性、活性和底物范围的催化剂体系的开发将极大地受益于这种多管齐下的方法。这些新系统的化学结构将在稍后阶段（5至10年时间框架）进一步调整，以解决其他复杂问题，包括选择性问题。从长远来看，这项研究计划将导致简单和可控的方法来制造碳-碳双键，使材料和有机化合物具有新的和增强的特性，包括具有强大的生物活性的药物。