Non-Covalent Immobilization Methods for Homogeneous Organic Catalysts

与产生废物的化学计量学方法相比，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和过渡金属为基础的。金属杂质在分离纯化后往往仍留在所需要的化合物中。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很低，而且对于经济上可行的工业应用来说，它们的处理要求太高。高活性非均相有机催化剂的应用和设计在精细化工和活性药物合成中有着广泛的影响，但由于反应性和范围的限制，迄今为止很少有催化剂能够实现工业实践。在接下来的五年里，MacQuarrie团队将采用一种创新的方法，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相性能的手性有机催化剂。催化剂不会被严格地束缚在表面上，提高了反应活性和对试剂的可用性，并且在催化剂放置的受限环境中，与均相类似物相比，立体控制将得到改善。这些材料将尽可能以廉价和绿色的方式制备，支撑材料将从高度有序的二氧化硅到生物炭等可再生资源。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）来实现几种有机催化剂的容易异质化。拟议的研究项目将主要由理学士学生完成，但研究生也将以辅助身份包括在内，以使小组多样化，并促进理学士学生考虑读研。所有学生都接受了独立操作现场设备的培训，并由理学士的高级学生、技术人员和博士后研究员与理学士配对进行项目，提供实验室监督。麦格理与生物能源公司和卢西堡海鲜公司建立了良好的工业合作关系，这两家公司都为博士后研究人员提供了实物资助，这对保证研究的一致性和促进学生监督至关重要，但他们的项目相当局限于与工业相关的工作。

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.