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，催化反应提供了有机化合物的绿色、高效和选择性合成。然而，许多催化转化是均相的并且是基于过渡金属的。在分离和纯化后，金属杂质通常保留在所需的化合物中。虽然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，并且它们的处理对于经济上可行的工业应用来说要求太高。高活性非均相有机催化剂的应用和设计在精细化学品和活性药物合成中具有广泛的影响，但迄今为止，由于有限的反应性和范围，很少有工业实践。 在接下来的五年里，MacQuarrie集团将实施一种创新的方法，通过离子结合催化剂和带电载体之间的电荷匹配来支持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上，从而提高了反应性和试剂的可用性，并且立体控制将优于均匀类似物，从而改善催化剂所处的受限环境。这些材料将以尽可能廉价和绿色的方式制备，载体将从高度有序的二氧化硅到可再生资源如生物炭。在本文中，我们将利用生物炭的带电性质（通过其保留的基于氧的官能团）来实现几类有机催化剂的容易的多相化。拟议的研究计划将主要与BSC学生完成，但研究生通过兼职身份包括在内，以使小组多样化，并促进BSC学生考虑研究生院。所有学生都接受了现场设备独立操作的培训，高级理学士学生，技术人员和博士后研究人员与项目上的理学士学生配对，提供实验室监督。MacQuarrie与BioEnergy Inc.建立了良好的工业合作关系。和路易斯安那州的海产品公司，两者都为博士后研究人员提供了实物资助，这是至关重要的，提供了研究的一致性和促进学生的监督，但他们的项目相当局限于工业相关的工作。