Bifunctional Organometallic Catalysis with Phosphines and N-Heterocyclic Carbenes

在这个由化学部化学催化项目资助的项目中，圣地亚哥州立大学的Douglas B. Grotjahn教授和Andrew L. Cooksy教授正在研究开发最佳催化剂的方法，这些催化剂可以制造出各种用途的有机化合物，例如药物化合物。人们正在设计和合成有机分子（配体），它们可以通过一个位点与金属原子结合，通过另一个位点与反应底物结合，并且正在测试一系列这些配体/金属组合的催化活性。人们正在研究这些催化剂发挥作用的基本分子水平步骤，目的是利用这些信息更好地设计下一代配体。由于催化作用占全球国内生产总值的三分之一和大部分商业化学产品和化学过程的过程，发现新的或改进的有机反应催化剂可以对经济发展和增长产生重大影响。在本研究项目的过程中，对本科生和研究生进行催化领域的培训，并开展了一项关于分子可视化的高中推广计划。Grotjahn教授和Cooksy教授正在使用酶的一些设计原理，特别是底物氢键和质子转移，目的是加速有机金属催化。含有供质子或氢键基团的配体正在被合成，并与各种金属前体结合形成金属配合物。研究的反应以无废加成或异构化反应为中心，有几个具体目标：(1)建立和应用烯烃异构化催化剂工具箱；(2)利用配体激活X-H；(3)加成反应催化剂的研制；(4)开发质子n -杂环碳化合物，这是一种较新的但很有前途的配体类，碳氮含有N-H片段，可以参与氢键或质子转移。该项目包括对学生进行有机和有机金属化学现代技术的一对一培训，包括核磁共振光谱、催化筛选和计算。提出的研究有可能为我们对双功能催化的更广泛理解增加新的机制见解。

In this project funded by the the Chemical Catalysis Program of the Chemistry Division, Professor Douglas B. Grotjahn and Professor Andrew L. Cooksy of San Diego State University are studying ways to develop the best catalysts for reactions that make organic compounds of interest for a variety of applications, such as pharmaceutical compounds. Organic molecules (ligands) are being designed and synthesized that can bind to a metal atom via one site and to a reacting substrate via another site, and a range of these ligand/metal combinations are being tested for catalytic activity. The fundamental, molecular level steps through which these catalysts function are being studied with the aim of utilizing this information to better design the next generation of ligands. Because catalysis accounts for processes that total one third of the global gross domestic product and a majority of the commercial chemical products and chemical processes, the discovery of new or improved catalysts for organic reactions can have a great impact on economic development and growth. During the course of this research project, undergraduate and graduate students are being trained in the field of catalysis, and a high school outreach program on molecular visualization is being carried out.Professors Grotjahn and Cooksy are using some of the design principles of enzymes, specifically substrate hydrogen bonding and proton transfer, with the aim of accelerating organometallic catalysis. Ligands containing proton-donating or hydrogen-bonding groups are being synthesized and combined with a variety of metal precursors to form metal complexes. The reactions being studied center on waste-free addition or isomerization reactions, with several specific goals: (1) building and applying a toolbox of alkene isomerization catalysts; (2) using ligands to enable X-H activation; (3) developing catalysts for addition reactions; (4) developing protic N-heterocyclic carbene compounds, a newer but promising ligand class with carbene nitrogens bearing an N-H moiety that can engage in hydrogen bonding or proton transfer. The project involves significant one-on-one training of students in modern techniques of organic and organometallic chemistry, including NMR spectroscopy, catalysis screening, and computation. The proposed research has the potential to add new mechanistic insight to our broader understanding of bifunctional catalysis.