Bifunctional Organometallic Catalysis with Phosphines and N-Heterocyclic Carbenes

膦和 N-杂环卡宾的双功能有机金属催化

• 批准号: 1464781
• 负责人: Douglas Grotjahn
• 金额: $ 51万
• 依托单位: San Diego State University Foundation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-05-01 至 2019-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464781&HistoricalAwards=false
• 关键词: Bifunctional; Organometallic; Catalysis; Phosphines; Heterocyclic

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.

在这个由化学系化学催化计划资助的项目中，道格拉斯教授B。Grotjahn和Andrew L.圣地亚哥州立大学的库克西正在研究开发最佳催化剂的方法，这些催化剂可以使有机化合物在各种应用中发挥作用，如药物化合物。 正在设计和合成有机分子（配体），其可以通过一个位点与金属原子结合，并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。 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。由于催化剂占全球国内生产总值的三分之一，占商业化学产品和化学工艺的大部分，因此发现新的或改进的有机反应催化剂对经济发展和增长具有重大影响。 在该研究项目的过程中，本科生和研究生正在接受催化领域的培训，并正在开展一项关于分子可视化的高中推广计划。Grotjahn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，旨在加速有机金属催化。含有质子供给或氢键基团的配体被合成并与各种金属前体结合以形成金属络合物。研究的重点是无废物加成或异构化反应，具体目标有：（1）建立和应用烯烃异构化催化剂工具箱;（2）利用配体实现X-H活化;（3）开发加成反应催化剂;（4）开发质子N-杂环卡宾化合物，一种较新的但有前途的配体类，具有带有N-H部分的卡宾氮，可以参与氢键或质子转移。该项目涉及学生在有机和有机金属化学的现代技术，包括核磁共振光谱学，催化筛选和计算显着的一对一的培训。拟议的研究有可能为我们更广泛地理解双功能催化添加新的机理见解。