Diol-Mediated Benzannulation for Polyaromatic Hydrocarbon (PAH) Construction

二醇介导的苯并环化用于多芳烃 (PAH) 的构建

• 批准号: 1855744
• 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: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855744&HistoricalAwards=false
• 关键词: Diol; Mediated; Benzannulation; Polyaromatic; Hydrocarbon

In this project, funded by the Chemical Synthesis Program of the Chemistry Division, Professor Michael J. Krische of the Department of Chemistry at the University of Texas at Austin is applying catalytic reactions developed in his laboratory to the construction of polycyclic aromatic hydrocarbons. Polycyclic aromatic hydrocarbons are used in commercial electronic display screens and show promise in a range of other applications, for example, high-speed electronics and solar cells. The project involves expertise spanning the fields of organic chemistry, homogenous transition metal catalysis, and materials chemistry. Professor Krische mentors and trains undergraduates, graduate students and postdoctoral research associates, including students from groups historically underrepresented in the sciences. Professor Krische founded and continues to co-organize a state-wide organic chemistry symposium in Texas, known as ?TEXSYN.? This annual event, which attracts 100 attendees, includes a poster session and short talks by undergraduate and graduate students, connecting students with leading researchers to design new routes to commodity and fine chemicals. Professor Michael J. Krische's laboratory has pioneered a new class of catalytic carbon carbon bond formations that directly convert lower alcohols to higher alcohols. These processes bypass the use of stoichiometric metals and discrete alcohol-to-carbonyl redox reactions, which are hazardous and contribute to waste generation. Based on this new reactivity pattern, diol-mediated benzannulation reactions were developed. Under the aegis of NSF support, this benzannulation methodology will be used to advance new strategies for the synthesis of polycyclic aromatic hydrocarbons and related nanographene materials, which are of significant importance in the growing field of molecular electronics. Whereas the field of polycyclic aromatic hydrocarbon synthesis is largely reliant on cross-coupling technology, this diol-mediated benzannulations could unlock broad and new polycyclic aromatic hydrocarbon chemical space.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在这个由化学部化学合成项目资助的项目中，德克萨斯大学奥斯汀分校化学系的Michael J. Krische教授将其实验室开发的催化反应应用于多环芳烃的构建。多环芳烃用于商业电子显示屏，并在高速电子和太阳能电池等一系列其他应用中显示出前景。该项目涉及有机化学、均相过渡金属催化和材料化学领域的专业知识。 Krische 教授指导和培训本科生、研究生和博士后研究员，其中包括来自历史上在科学领域代表性不足的群体的学生。 Krische 教授在德克萨斯州创办并继续共同组织全州范围的有机化学研讨会，称为“TEXSYN”。这项年度活动吸引了 100 名与会者，包括海报会议以及本科生和研究生的简短演讲，将学生与领先的研究人员联系起来，设计商品和精细化学品的新路线。 Michael J. Krische 教授的实验室开创了一种新型催化碳碳键形成方法，可将低级醇直接转化为高级醇。这些过程绕过了化学计量金属的使用和离散的醇到羰基氧化还原反应，这些反应是危险的并且会导致废物产生。基于这种新的反应模式，开发了二醇介导的苯并环化反应。在 NSF 的支持下，这种苯并环化方法将用于推进合成多环芳烃和相关纳米石墨烯材料的新策略，这在不断发展的分子电子学领域具有重要意义。尽管多环芳烃合成领域在很大程度上依赖于交叉偶联技术，但这种二醇介导的苯并环化可以解锁广泛且新的多环芳烃化学空间。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准。

项目成果

Chemical Tuning of Exciton versus Charge-Transfer Excited States in Conformationally Restricted Arylene Cages

构象限制的亚芳基笼中激子与电荷转移激发态的化学调节

• DOI: 10.1021/jacs.1c08176
• 发表时间: 2021-11
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Lewis, Taylor N.;Tonnelé, Claire;Shuler, William G.;Kasun, Zachary A.;Sato, Hiroki;Berges, Adam J.;Rodriguez, Jacob R.;Krische, Michael J.;Casanova, David;Bardeen, Christopher J.
• 通讯作者: Bardeen, Christopher J.

Synthesis and Photophysical Properties of Soluble N‐Doped Rubicenes via Ruthenium‐Catalyzed Transfer Hydrogenative Benzannulation

钌催化转移氢化苯环化合成可溶性N掺杂Rubicenes及其光物理性质

• DOI: 10.1002/chem.202100134
• 发表时间: 2021-02
• 期刊: Chemistry – A European Journal
• 作者: Shuler, William G.;Parvathaneni, Sai P.;Rodriguez, Jacob B.;Lewis, Taylor N.;Berges, Adam J.;Bardeen, Christopher J.;Krische, Michael J.
• 通讯作者: Krische, Michael J.

Ruthenium-Catalyzed Cycloadditions to Form Five-, Six-, and Seven-Membered Rings

钌催化环加成形成五元环、六元环和七元环

• DOI: 10.1021/acs.chemrev.0c01133
• 发表时间: 2021-04-14
• 期刊: Chemical Reviews
• 影响因子: 62.1
• 作者: Doerksen RS;Hodík T;Hu G;Huynh NO;Shuler WG;Krische MJ
• 通讯作者: Krische MJ

Benzannulation through Ruthenium(0)‐Catalyzed Transfer Hydrogenative Cycloaddition: Precision Synthesis and Photophysical Characterization of Soluble Diindenoperylenes

通过钌(0)进行苯并环化——催化转移氢化环加成：可溶性二茚并苝的精密合成和光物理表征

• DOI: 10.1002/chem.202001731
• 发表时间: 2020-05
• 期刊: Chemistry – A European Journal
• 作者: Suravarapu, Sankar Rao;Parvathaneni, Sai Prathima;Bender, Jon A.;Roberts, Sean T.;Krische, Michael J.
• 通讯作者: Krische, Michael J.

Triple Helical Ir(ppy) 3 Phenylene Cage Prepared by Diol‐Mediated Benzannulation: Synthesis, Resolution, Absolute Stereochemistry and Photophysical Properties

二醇介导苯环化制备三螺旋Ir(ppy) 3 亚苯基笼：合成、拆分、绝对立体化学和光物理性质

• DOI: 10.1002/chem.201902122
• 发表时间: 2019-05
• 期刊: Chemistry – A European Journal
• 作者: Sato, Hiroki;Blemker, Michelle A.;Hellinghausen, Garrett;Armstrong, Daniel W.;Nafie, Jordan W.;Roberts, Sean T.;Krische, Michael J.
• 通讯作者: Krische, Michael J.