Alkynes As High-Energy Carbon-Rich Functionality For Synthesis Of Polyaromatics

炔烃作为高能富碳官能团用于合成聚芳烃

• 批准号: 1800329
• 负责人: Igor Alabugin
• 金额: $ 50万
• 依托单位: Florida State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-07-01 至 2021-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1800329&HistoricalAwards=false
• 关键词: Alkynes; Energy; Carbon; Rich; Functionality

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Igor Alabugin. Professor Alabugin is a faculty member in the Department of Chemistry and Biochemistry at the Florida State University. He is developing new ways to prepare precisely shaped and functionalized structures of graphene (a flat sheet containing only carbon atom). The goal of the project is to provide the missing synthetic tools needed to construct new molecules with interesting optoelectronic properties. To do this, the high energy and unique, tunable reactivity of carbon-rich precursors for will be used to develop strategies that build the shaped graphene structures from smaller pieces. Key to this effort are cascade reactions that form multiple bonds and unite multiple cyclic unites in a single operation. By splicing together the smaller structure in a controlled fashion, the shape of the larger object can be controlled more precisely. The results will be disseminated in the PI's publications and outreach activities, including participation in public lectures, scientific symposia, giving talks at industrial, undergraduate, and graduate institutions, as well as recording educational videos at the GEOSET studio at Florida State University.The intellectual merit of this research is in leveraging electronic factors that control alkyne cyclizations for the development of efficient routes to conjugated carbon nanostructures with predesigned shape and functionality. In this approach, oilgoalkyne chains of varying sizes, equipped with different substituents, are built in a modular fashion and then "zipped" up via a cascade of fast and efficient radical cyclizations. Selectivity of initial radical attack on the multifunctional substrates is controlled by the presence of a "traceless directing group" that is removed in the course of the one-pot process. By the choice of the relay functional groups and the terminal pi-system, the final step of the cascade can be controlled, so that either a five- or a six-membered rings is formed. In particular, this work is developing a suite of peri-cyclizations based on a combination of traceless directing groups, cyclization at the "zigzag edge" of acene subunits, and fragmentations. This approach opens access to unusual aromatics and conjugated persistent radicals. The broader impact include the applications of the new carbon-rich conjugated molecules as components in the design of optoelectronic materials, energy storage devices, sensors, transistors, solar cells, polymer composites etc. The educational plan includes providing advanced research training to students of different backgrounds, including students from the Florida historically black universities. The scholarly findings will be presented in scientific journals, conferences and incorporated in the mini-courses on stereoelectronic effects.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.

化学系的化学合成计划支持Igor Alabugin教授的项目。Alabugin教授是佛罗里达州立大学化学和生物化学系的教员。 他正在开发新的方法来制备石墨烯（一种仅含碳原子的平板）的精确形状和功能化结构。该项目的目标是提供构建具有有趣光电特性的新分子所需的缺失合成工具。为了做到这一点，高能量和独特的，可调的富碳前体反应性将用于开发从较小的碎片构建成型石墨烯结构的策略。这一努力的关键是级联反应，形成多个键，并在一个单一的操作团结多个环状单位。通过以受控的方式将较小的结构拼接在一起，可以更精确地控制较大物体的形状。研究结果将在PI的出版物和外联活动中传播，包括参加公开讲座、科学研讨会、在工业、本科和研究生机构发表演讲，以及在佛罗里达州立大学的GEOSET工作室录制教育视频。这项研究的智力价值在于利用控制炔环化的电子因素来开发共轭的有效途径。具有预先设计的形状和功能的碳纳米结构。在这种方法中，不同大小的、配备有不同取代基的油基炔链以模块化的方式构建，然后通过快速有效的自由基环化级联“压缩”。对多功能底物的初始自由基攻击的选择性通过在一锅法过程中除去的“无痕导向基团”的存在来控制。通过选择中继官能团和末端π系统，可以控制级联的最后步骤，从而形成五元环或六元环。特别是，这项工作正在开发一套基于无痕导向基团，环化并苯亚基的“锯齿形边缘”，和碎片的组合的围环化。这种方法打开了获得不寻常的芳香族化合物和共轭持久自由基的途径。 更广泛的影响包括新的富碳共轭分子作为组件在光电材料，储能设备，传感器，晶体管，太阳能电池，聚合物复合材料等的设计中的应用。教育计划包括为不同背景的学生提供先进的研究培训，包括来自佛罗里达历史上的黑人大学的学生。学术研究成果将在科学期刊、会议上发表，并纳入立体电子效应的迷你课程。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的知识价值和更广泛的影响审查标准进行评估来支持。

项目成果

Strain and stereoelectronics in cycloalkyne click chemistry

• DOI: 10.1016/j.mencom.2019.05.001
• 发表时间: 2019-05-01
• 期刊: MENDELEEV COMMUNICATIONS
• 影响因子: 1.9
• 作者: Harris, Trevor;Alabugin, Igor V.
• 通讯作者: Alabugin, Igor V.

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

• DOI: 10.1021/jacs.1c02249
• 发表时间: 2021-04-20
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Yaremenko，Ivan A.;Belyakova，Yulia Yu;Terent'ev，Alexander O.
• 通讯作者: Terent'ev，Alexander O.

Organocatalytic sulfoxidation

• DOI: 10.1016/j.tet.2020.131784
• 发表时间: 2021-01-08
• 期刊: TETRAHEDRON
• 影响因子: 2.1
• 作者: Davidson, Stuart C.;Gomes, Gabriel dos Passos;Tomkinson, Nicholas C. O.
• 通讯作者: Tomkinson, Nicholas C. O.

Controlled Evolution of the Cope Rearrangement: Transition from Concerted to Interrupted and Aborted Pericyclic Reactions Regulated by a Switch Built from an Intramolecular Frustrated Lewis Pair

Cope重排的受控演化：由分子内受阻路易斯对构建的开关调节从协同反应到中断和中止的周环反应的转变

• DOI: 10.1021/acs.joc.9b02633
• 发表时间: 2019
• 期刊: The Journal of Organic Chemistry
• 作者: Vidhani, Dinesh V.;Alabugin, Igor V.
• 通讯作者: Alabugin, Igor V.

Impact of Excited-State Antiaromaticity Relief in a Fundamental Benzene Photoreaction Leading to Substituted Bicyclo[3.1.0]hexenes

• DOI: 10.1021/jacs.9b13769
• 发表时间: 2020-06-24
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Slanina, Tomas;Ayub, Rabia;Ottosson, Henrik
• 通讯作者: Ottosson, Henrik