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项目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教授的方法涉及到廉价、丰富的石化原料（二烯）与可再生原料（二醇）的无副产物耦合。多环芳烃物质是在反应产物脱水后形成的，这意味着水是唯一的化学副产物。本项目处于有机化学、有机金属化学和材料化学的交叉点，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。随着德克萨斯州西班牙裔人口的增长，克里什教授的小组在教育和培训学生方面发挥了重要作用，这些学生来自历史上在科学领域代表性不足的群体。外展活动包括由绿色化学和催化中心主办的年度研究专题讨论会，由Krische教授领导，由催化领域的主要化学家举办讲座，以及主办本科生、研究生和博士后科学家的海报会议。Krische实验室正在开拓一种广泛的新型催化碳-碳（C-C）键形成，它融合了催化氢化和羰基加成的特征，代表了氢甲酰化之外的第一个“C-C键形成氢化”。这种新的反应模式是钌(0)催化的二烯-二醇[4+2]环加成的基础。这种无副产物的转化被用于推进新的苯并制制多环芳烃（PAHs）的技术。环芳烃、聚苯乙烯、荧光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，自联芳基交联技术出现以来，多环芳烃的构建领域基本没有变化。就像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-二醇苄环化可能开启新的多环芳烃化学空间，广泛影响碳纳米同素异形体和分子器件界的研究。该教育计划包括由绿色化学和催化中心主办的年度研究研讨会，由Krische教授领导，由催化领域的主要化学家举办讲座，以及由本科生、研究生和博士后科学家举办的海报会议。

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.