Non-Covalent Immobilization Methods for Homogeneous Organic Catalysts

均相有机催化剂的非共价固定方法

• 批准号: RGPIN-2018-06086
• 负责人: Macquarrie, Stephanie
• 金额: $ 1.75万
• 依托单位: Cape Breton University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2019
• 资助国家: 加拿大
• 起止时间: 2019-01-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=679887
• 关键词: Non; Covalent; Immobilization; Methods; Homogeneous

Catalytic reactions provide green, efficient, and selective syntheses of organic compounds when compared to waste-generating stoichiometric methods. However, many catalytic transformations are homogeneous and transition metal based. Metal impurities often remain in the desired compound after isolation and purification. Although selective homogeneous organocatalysts can be used, their activities and stabilities are often low, and their handling too demanding for economically viable industrial applications. The application and design of highly active heterogeneous organic catalysts has broad impacts in fine chemical and active pharmaceutical synthesis, yet to-date very few have made it to industrial practice due to limited reactivity and scope. Over the next five years the MacQuarrie group will implement an innovative method of supporting an array of chiral organic catalysts with enhanced homogeneous properties via charge matching between the ionically bound catalyst and the charged supports. The catalyst will not be rigidly bound to the surface enhancing reactivity and availability to reagents and stereocontrol will be improved over homogeneous analogues do to the confined environments the catalysts are placed in. The materials will be prepared in as inexpensive and green a manner as possible and the supports will range from highly ordered silicas to renewable resources such as biochar. Herein, we will take advantage of the charged nature of biochar (through its retained oxygen based functional groups) to enable facile heterogenization of several classes of organocatalysts. The proposed research program will be completed primarily with BSc students, however graduate students are included via adjunct status, to diversify the group and promote BSc students to consider graduate school. All students are trained for independent operation of on-site equipment, and senior BSc students, technicians, and postdoctoral researchers are paired with the BSc students on the projects, providing laboratory supervision. MacQuarrie has a well-established industrial collaboration with BioEnergy Inc. and the Lousibourg Seafoods Inc., both of which have provided in-kind funding for a postdoctoral researcher which is of paramount importance, providing consistency in research and facilitating student supervision, but their projects are fairly limited to industrially relevant work.

与产生废物的化学计量方法相比，催化反应提供了绿色、高效和选择性的有机化合物合成。然而，许多催化转化是均相的并且基于过渡金属。分离和纯化后，金属杂质通常保留在所需化合物中。尽管可以使用选择性均相有机催化剂，但它们的活性和稳定性通常较低，并且对于经济上可行的工业应用来说，它们的处理要求过高。高活性多相有机催化剂的应用和设计对精细化工和活性药物合成具有广泛影响，但迄今为止，由于反应活性和范围有限，很少有催化剂能够进入工业实践。 在接下来的五年中，麦格理集团将实施一种创新方法，通过离子键合催化剂和带电载体之间的电荷匹配来负载一系列具有增强均匀特性的手性有机催化剂。催化剂不会严格地结合到表面，从而增强反应性和试剂的可用性，并且立体控制将比催化剂所处的受限环境的均相类似物得到改善。材料将以尽可能便宜和绿色的方式制备，载体的范围从高度有序的二氧化硅到可再生资源，如生物炭。在这里，我们将利用生物炭的带电性质（通过其保留的氧基官能团）来实现几类有机催化剂的轻松异质化。拟议的研究计划将主要由理学学士学生完成，但研究生也以兼职身份纳入其中，以实现群体多元化并促进理学学士学生考虑研究生院。所有学生都接受了独立操作现场设备的培训，高级理学士学生、技术人员和博士后研究人员与理学士学生在项目上配对，提供实验室监督。 MacQuarrie 与 BioEnergy Inc. 和 Lousibourg Seafoods Inc. 建立了良好的行业合作关系，这两家公司都为博士后研究员提供了至关重要的实物资助，提供了研究的一致性并促进了学生的监督，但他们的项目相当局限于与行业相关的工作。