Catalytic Diene-Diol Benzannulation for Polycyclic Aromatic Hydrocarbon Construction

催化二烯二醇苯并环化反应构建多环芳烃

• 批准号: 1565688
• 负责人: Michael Krische
• 金额: $ 48万
• 依托单位: University of Texas at Austin
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-05-01 至 2020-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565688&HistoricalAwards=false
• 关键词: Catalytic; Diene; Diol; Benzannulation; Polycyclic

The Chemical Synthesis Program of the NSF Chemistry Division supports the research of Professor Michael J. Krische in the Department of Chemistry at the University of Texas at Austin. Professor Krische and his students are developing novel, green catalytic methods for the construction of PAH (polycyclic aromatic hydrocarbon) - materials that are used broadly in molecular electronics. Professor Krische's method involves the byproduct-free coupling of inexpensive, abundant petrochemical feedstocks (dienes) with a renewable feedstock (diols). PAH materials are formed upon dehydration of the reaction products, meaning water is the only chemical byproduct. This project lies at the interface of organic, organometallic and materials chemistry and provides a suitable forum for the education of undergraduate, graduate and postdoctoral scientists. With the growing Hispanic demographic in Texas, Professor Krische's group has played a strong role in the education and training of students from groups historically underrepresented in science. Outreach activities include an annual research symposia sponsored by the Center for Green Chemistry and Catalysis led by Professor Krische, which features lectures by leading chemists in the field of catalysis, as well as poster sessions hosting undergraduate, graduate and postdoctoral scientists.The Krische laboratory is pioneering a broad, new class of catalytic carbon-carbon (C-C) bond formations that merge the characteristics of catalytic hydrogenation and carbonyl addition, representing the first "C-C bond forming hydrogenations" beyond hydroformylation. This new pattern of reactivity is the basis of a ruthenium(0) catalyzed diene-diol [4+2] cycloaddition. This byproduct-free transformation is being used to advance new benzannulation technology for the construction of Polycyclic Aromatic Hydrocarbons (PAHs). Acenes, polyphenylenes, fluoranthenes and carbon nano-allotropes - there is great interest in such PAH materials in the field of molecular electronics. However, since the advent of biaryl cross-coupling technology, the field of PAH construction has remained largely unchanged. Just as biaryl cross-coupling technology revolutionized PAH construction, diene-diol benzannulation may unlock new PAH chemical space, broadly impacting research across the carbon nano-allotrope and molecular device communities. The educational plan includes annual research symposia sponsored by the Center for Green Chemistry and Catalysis led by Professor Krische, which features lectures by leading chemists in the field of catalysis, as well as poster sessions hosting undergraduate, graduate and postdoctoral scientists.

NSF 化学部的化学合成计划支持德克萨斯大学奥斯汀分校化学系 Michael J. Krische 教授的研究。 Krische 教授和他的学生正在开发新颖的绿色催化方法来构建 PAH（多环芳烃）——广泛用于分子电子学的材料。 Krische 教授的方法涉及廉价、丰富的石化原料（二烯）与可再生原料（二醇）的无副产物偶联。 PAH 材料是在反应产物脱水时形成的，这意味着水是唯一的化学副产品。该项目位于有机化学、有机金属化学和材料化学的交叉领域，为本科生、研究生和博士后科学家的教育提供了合适的论坛。随着德克萨斯州拉美裔人口的不断增长，克里斯切教授的团队在教育和培训历史上在科学领域代表性不足的群体的学生方面发挥了重要作用。外展活动包括由 Krische 教授领导的绿色化学与催化中心主办的年度研究研讨会，其中包括催化领域顶尖化学家的讲座，以及举​​办本科生、研究生和博士后科学家的海报会议。Krische 实验室是开创了一种广泛的新型催化碳-碳（C-C）键形成，融合了催化氢化和羰基加成的特征，代表了第一个“C-C键形成氢化”加氢甲酰化。这种新的反应模式是钌(0)催化二烯二醇[4+2]环加成的基础。这种无副产品的转化正被用来推进用于构建多环芳烃（PAH）的新苯并环化技术。并苯、聚苯撑、荧蒽和碳纳米同素异形体——分子电子学领域对此类多环芳烃材料有着极大的兴趣。然而，自从联芳交叉偶联技术出现以来，PAH 构建领域基本保持不变。正如联芳交叉偶联技术彻底改变了 PAH 结构一样，二烯二醇苯并环化可能会开启新的 PAH 化学空间，广泛影响碳纳米同素异形体和分子器件领域的研究。该教育计划包括由 Krische 教授领导的绿色化学和催化中心主办的年度研究研讨会，其中包括催化领域领先化学家的讲座，以及举​​办本科生、研究生和博士后科学家的海报会议。