Reinventing Benzannulations: Electro-, Photo-, and Radical Approaches for Fusing Benzene and Cyclopentadiene Rings into Polyaromatics

重塑苯环化：将苯环和环戊二烯环融合成聚芳烃的电、光和自由基方法

• 批准号: 2102579
• 负责人: Igor Alabugin
• 金额: $ 55万
• 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: 2021
• 资助国家: 美国
• 起止时间: 2021-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102579&HistoricalAwards=false
• 关键词: Reinventing; Benzannulations; Electro; Photo; Radical

In this project, funded jointly by the Chemical Structure, Dynamics, & Mechanisms B and Chemical Synthesis Programs of the Division of Chemistry, Professor Igor Alabugin at Florida State University will address fundamental questions in the structure and synthesis of complex polycyclic aromatic compounds. Molecular systems that allow precise control of atomic structure and energy levels at the sub-nanospace can serve as components of opto-electronic materials, energy storage devices, sensors, transistors, solar cells, functional polymers etc. This research aims to develop efficient synthetic approaches to complex polycyclic aromatic systems via fusions of modularly assembled precursors into new carbon-rich graphene substructures. New concepts for the design of complex ring synthesis drive this project. This work combines computational and experimental components to allow training of specialists in each area. The project will provide researchers at the undergraduate, graduate and postdoctoral levels with an opportunity to integrate learning and discovery. The results will be disseminated through publications and outreach activities, including participation in public lectures, scientific symposia, giving talks at industries, undergraduate and graduate institutions, as well as recording educational videos.This proposal sets out to develop new approaches to the rapid construction of functionalized polycyclic aromatics by using the residual strain of helicenes and selectively generated high-energy reactive intermediates such as antiaromatic species, excited states and vinyl radicals. Furthermore, the Alabugin research team is aiming to complement available purely hexagonal graphenic networks with selectively introduced pentagonal fusions as a way to design negatively charged carbon-rich materials. Professor Alabugin and his co-workers will also work to expand the scope of the double-annulation reactions under study such that, in a one-pot operation, the transformation effectively converts monosubstituted benzenes into pyrenes and pyrene analogues with precisely placed functional groups and heteroatoms. If successful, this multi-faceted transformation would open up one of the most efficient examples of complex functional group-tolerant benzannulation chemistry.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.

在这个项目中，由化学部的化学结构，动力学，机理B和化学合成计划共同资助，佛罗里达州立大学的Igor Alabugin教授将解决复杂多环芳族化合物的结构和合成中的基本问题。 允许精确控制原子结构和能级的亚纳米空间的分子系统可以作为光电材料，储能器件，传感器，晶体管，太阳能电池，功能聚合物等的组成部分。本研究旨在通过将模块化组装的前体融合到新的富碳石墨烯子结构中，开发复杂多环芳香族系统的有效合成方法。复杂环合成设计的新概念推动了这个项目。这项工作结合了计算和实验的组成部分，允许在每个领域的专家培训。该项目将为本科生、研究生和博士后水平的研究人员提供一个整合学习和发现的机会。将通过出版物和外联活动传播成果，包括参加公开讲座、科学研讨会、在工业界、本科和研究生院发表演讲，以及录制教育视频。该提案旨在开发新的方法，通过使用螺旋烯的残余菌株和选择性生成的高-能量反应性中间体，如反芳族物质、激发态和乙烯基自由基。此外，Alabugin研究小组的目标是通过选择性地引入五边形融合来补充现有的纯六边形石墨烯网络，作为设计带负电荷的富碳材料的一种方式。Alabugin教授和他的同事还将努力扩大研究中的双环化反应的范围，以便在一锅操作中，转化有效地将单取代苯转化为具有精确放置的官能团和杂原子的芘和芘类似物。 如果成功的话，这种多方面的转变将开辟一个最有效的例子，复杂的功能基团耐受benzannulation化学。这个奖项反映了NSF的法定使命，并已被认为是值得的支持，通过评估使用基金会的知识价值和更广泛的影响审查标准。

项目成果

Localized Antiaromaticity Hotspot Drives Reductive Dehydrogenative Cyclizations in Bis- and Mono-Helicenes

局部反芳香性热点驱动双螺旋烯和单螺旋烯的还原脱氢环化

• DOI: 10.1021/jacs.2c03681
• 发表时间: 2022
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Zhou, Zheng;Egger, Dominic T.;Hu, Chaowei;Pennachio, Matthew;Wei, Zheng;Kawade, Rahul K.;Üngör, Ökten;Gershoni-Poranne, Renana;Petrukhina, Marina A.;Alabugin, Igor V.
• 通讯作者: Alabugin, Igor V.

A Swiss Army knife for surface chemistry

表面化学领域的瑞士军刀

• DOI: 10.1126/science.abq2622
• 发表时间: 2022
• 期刊: Science
• 影响因子: 56.9
• 作者: Alabugin, Igor;Hu, Chaowei
• 通讯作者: Hu, Chaowei

Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals

• DOI: 10.1021/acs.orglett.2c01356
• 发表时间: 2022-06-03
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Kuhn, Leah;Vil, Vera A.;V. Alabugin, Igor
• 通讯作者: V. Alabugin, Igor

Remote Stereoelectronic Effects in Pyrrolidone- and Caprolactam-Substituted Phenols: Discrepancies in Antioxidant Properties Evaluated by Electrochemical Oxidation and H-Atom Transfer Reactivity

• DOI: 10.1021/acs.joc.2c00207
• 发表时间: 2022-04-15
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Akyeva, Anna Ya;Kansuzyan, Artem, V;Syroeshkin, Mikhail A.
• 通讯作者: Syroeshkin, Mikhail A.

AIBN as an Electrophilic Reagent for Cyano Group Transfer

• DOI: 10.1021/acs.joc.2c02859
• 发表时间: 2023-02-08
• 期刊: JOURNAL OF ORGANIC CHEMISTRY
• 影响因子: 3.6
• 作者: Elliott，Quintin;Alabugin，Igor V.
• 通讯作者: Alabugin，Igor V.