Non-Covalent Immobilization Methods for Homogeneous Organic Catalysts

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和基于过渡金属的。金属杂质在分离和提纯后往往残留在所需化合物中。尽管可以使用选择性的均相有机催化剂，但它们的活性和稳定性往往很低，而且它们的操作要求太高，不适合经济上可行的工业应用。高活性多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，但由于反应活性和范围有限，迄今很少有催化剂进入工业实践。在接下来的五年里，麦夸里团队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，支持一系列具有增强的均质性质的手性有机催化剂。催化剂不会被严格地束缚在表面上，提高了反应性和试剂的可用性，立体控制将比均匀的类似物更好，对催化剂所处的受限环境也是如此。这些材料将以尽可能便宜和绿色的方式制备，载体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(通过其保留的含氧基官能团)来实现几类有机催化剂的轻松异构化。拟议的研究计划将主要与理科学士学生一起完成，但研究生将通过兼职身份包括在内，以使群体多样化，并促进理科理科学生考虑读研究生。所有学生都接受了独立操作现场设备的培训，高级理科学生、技术员和博士后研究人员与理科学生在项目中配对，提供实验室监督。麦夸里与BioEnergy Inc.和Lousiburg Seafoods Inc.有着良好的工业合作关系，这两家公司都为一名博士后研究人员提供了实物资助，这一点至关重要，提供了研究的一致性，并促进了学生的监督，但他们的项目仅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.