New periodic mesoporous organic silicas for catalysis

麦夸里研究计划通过合成和表征由脯氨酸和N-杂环卡宾衍生骨架组成的高度组织化的功能化纳米材料，将化学、纳米材料和催化这两个独特的领域结合在一起。所得到的固定化有机催化剂将用于C-C键的形成反应，如Aldol反应或Stetter反应，以测试催化剂的适用性和重复使用，并找到最佳反应条件。这些高度有序的有机硅具有均匀的孔隙率，允许反应物自由进入催化活性微环境，从而实现高效的对映选择性。这种新型有机硅氧烷单体将通过简单的模块化合成方法制备，并通过六个共价键直接结合到三维惰性、热稳定性和无毒的二氧化硅骨架中，导致有机组分完全均匀分布，具有较强的锚固点。 这一研究计划促进了跨学科科学之间的合作，为本科生研究人员提供了与工业相关的研究经验，并接触到了化学的多学科领域。拟议研究的个别项目是专门设计的，具有针对性的项目，非常适合以本科生为主的机构的学生。最初的工作将集中在有机催化反应中使用的基于脯氨酸和N-杂环卡宾的材料，研究范围可以扩大到包括用于过渡金属催化的过渡金属的添加，如钯(Pd)或铑(Rh)。本文提出的新型催化材料有可能给催化工业带来革命性的变化，减少化学废物，并为均相过渡金属催化剂提供无金属替代品。

The MacQuarrie research program combines two unique fields of chemistry, nanomaterials and catalysis by synthesizing and characterizing highly organized functionalized nanomaterials composed of proline and N-heterocyclic carbene-derived skeletons. The resulting immobilized organocatalysts will be invesitgated in C-C bond forming reactions such as the aldol or Stetter reaction to test the applicability and reusability of the catalysts and discover optimum reaction conditions. These highly ordered organosilicas will have uniform porosity, permitting reactants to freely access the catalytically active microenvironments leading to highly effective enantioselection. The novel organic siloxane monomers will be prepared through a simple modular synthetic approach and directly incorporated into three-dimensional inert, thermally stable and non-toxic silicon oxide backbone through six covalent bonds, leading to complete homogeneous distribution of the organic components with strong anchoring points. This research program facilitates the collaboration between interdisciplinary sciences providing undergraduate student researchers with industrially relevant research experience and exposure to multidisciplinary areas of chemistry. The individual projects of the proposed research are specifically designed with targeted projects well suited for students at a primarily undergraduate institution. Initial efforts will focus on proline and N-heterocyclic carbene based materials utilized in organocatalytic reactions, the research can be extended to include the addition of transition metals such as palladium (Pd) or rhodium (Rh) for use in transition-metal based catalysis as well. The new catalytic materials proposed herein have the potential to revolutionize the catalysis industry, reduce chemical waste and provide metal-free alternatives to homogeneous transition metal based catalysts.