Catalytic Diene-Diol Benzannulation for Polycyclic Aromatic Hydrocarbon Construction

美国国家科学基金会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的Michael J.Krische教授的研究。Krische教授和他的学生正在开发构建PAH(多环芳烃)的新型绿色催化方法--这种材料在分子电子学中得到了广泛的应用。Krische教授的方法涉及廉价、丰富的石化原料(双烯)与可再生原料(二元醇)的无副产品耦合。多环芳烃物质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、有机金属和材料化学的交界处，为本科生、研究生和博士后科学家的培养提供了一个合适的论坛。随着德克萨斯州西语裔人口的不断增长，克里斯基教授的团队在教育和培训学生方面发挥了强大的作用，这些学生来自历史上在科学界代表性不足的群体。推广活动包括由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，该研讨会的特色是催化领域的领先化学家的演讲，以及招待本科生、研究生和博士后科学家的海报会议。Krische实验室正在开创一种广泛的新类别的催化碳-碳(C-C)键形成，它融合了催化氢化和羰基加成的特点，是氢甲酰化以外的第一个“C-C键形成氢化”。这种新的反应模式是Ru(0)催化的二烯-二醇[4+2]环加成反应的基础。这种无副产物转化正被用于推进新的苯环化技术，以构建多环芳烃(PAHs)。苯、多苯、荧蒽和碳纳米同素异形体--这类多环芳烃材料在分子电子学领域引起了极大的兴趣。然而，自从联芳基交叉偶联技术问世以来，多环芳烃的构筑领域基本上没有变化。正如联芳基交叉偶联技术彻底改变了多环芳烃的结构一样，二烯-二酚苯环化反应可能会打开新的多环芳烃化学空间，对碳纳米同素异形体和分子装置领域的研究产生广泛影响。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演讲，以及招待本科生、研究生和博士后科学家的海报会议。

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.