Hexadehydro-Diels-Alder (HDDA) Reaction-Enabled Synthesis of Structurally Elaborate, Polycyclic Aromatic Compounds

六氢狄尔斯-阿尔德 (HDDA) 反应合成结构精巧的多环芳香族化合物

基本信息

批准号：
2155042
负责人：
Thomas Hoye
金额：
$ 52.5万
依托单位：
University of Minnesota-Twin Cities
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2022
资助国家：
美国
起止时间：
2022-09-01 至 2025-08-31
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2155042&HistoricalAwards=false
关键词：
Hexadehydro Diels Alder HDDA Reaction

项目摘要

With the support of the Chemical Synthesis (SYN) Program in the Division of Chemistry, Professor Thomas Hoye of the University of Minnesota is studying the use of a versatile new method for chemical synthesis known as the hexadehydro-Diels-Alder (HDDA) reaction. The HDDA reaction requires merely the simple heating of an appropriately designed precursor (a reactant known as a triyne) to produce a highly reactive species known as a benzyne. In turn, this intermediate can engage myriad types of “trapping agents,” often resulting in unprecedented types of chemical transformation. The funded research focuses on using the HDDA reaction as a tool to discover new ways to build molecules known as polycyclic aromatics. Compounds of this class often exhibit photochemical and photophysical properties critical for the operation of modern optoelectronic devices that are of great value to society; for example, organic light emitting diodes (OLEDs), which are used in energy efficient displays and lighting units, and photovoltaic cells, which are used for the conversion of solar energy into electricity. In addition to facilitating the preparation of polycyclic aromatics, pursuit of the project aims is anticipated to advance both fundamental understanding of various new types of chemical transformations as well as providing the means and inspiration to access previously elusive types of chemical structures. A number of significant broader impacts of benefit to a wider group of stakeholders – including students, instructors, and the broader scientific community – are planned. Of particular note are (1) an activity dubbed “Vignettes in Physical Organic Chemistry” in which Professor Hoye and his coworkers will prepare (and make available on a curated website) pedagogically valuable documents of historically important developments in the field of mechanistic organic chemistry, and (2) the development and dissemination of tutorial tips and tricks of practical value to the users of NMR spectroscopy, the single most valuable and powerful tool for analyzing organic reactions and structures.This award is enabling the Hoye research group to continue to capitalize on the capacity of the HDDA reaction to facilitate concise and efficient elaborations of highly conjugated polycyclic aromatics. The new methods and strategies for the syntheses of such compounds are the most important outcomes that are anticipated to result from this project but fundamentally important mechanistic knowledge will likely also emerge. Specific topics to be explored include naphthalene- and anthracene-templated HDDA reactions, intra-annular HDDA reactions, “propagating HDDA reactions” for the synthesis of conjugated polymers, and the use of an iterative exponential growth strategy to produce discreet polyyne substrates designed to undergo long sequences of “domino HDDA reactions” leading to oligomeric linear polyacenes. Professor Hoye holds major teaching awards that recognize his career-long commitment to the education of students at both the undergraduate and graduate levels. Broader activities supported by this project will benefit chemistry research students at multiple levels. The scientific advances have the possibility of opening new avenues for pursuit by materials scientists who use organic electronic and photonic compounds in the settings of light-emitting diodes, photovoltaics, and solar cells, applications that have a large potential for societal impact.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.

在化学合成计划（SYN）方案的支持下，明尼苏达大学的托马斯·霍伊教授正在研究使用多种化学合成的新方法，称为六卫hhydro-diels-alder（HDDA）反应。 HDDA反应仅需要简单地加热适当设计的前体（称为Triyne的反应物），以产生一种高反应性的物种，称为苯甲。反过来，该中间体可以吸引多种类型的“捕获剂”，通常会导致前所未有的化学转化类型。资助的研究重点是使用HDDA反应作为发现新方法来构建称为多环芳烃的新方法。该类别的化合物通常暴露于光化学和光物理特性对于对社会具有巨大价值的现代光电设备的运行至关重要。例如，用于节能的显示和照明单元和光伏电池的有机光发射二极管（OLEDS），用于将太阳能转化为电能。除了支持多环芳香剂的制备外，对项目的追求还预计，还可以促进对各种新型化学转化类型的基本理解，并为访问以前难以捉摸的化学结构类型的手段和灵感提供。计划对更广泛的利益相关者（包括学生，讲师和更广泛的科学界）产生更广泛的利益影响。（1）一项被称为“物理有机化学中的小插曲”的活动，其中Hoye教授和他的同事将在策划的机械有机化学领域中为历史上重要发展的教学上有价值的有价值的文档做好准备（并在机械性有机化学领域提供），以及（2）有价值的大多数工具和技巧，以实践和技巧为NMR的实践价值和技巧，以实践和技巧为单位。分析有机反应和结构。该奖项使Hoye研究小组能够继续利用HDDA反应的能力，以促进高度共轭多环芳香族剂的简洁有效阐述。此类化合物合成的新方法和策略是最重要的结果，预计该项目将由该项目产生，但从根本上重要的机械知识也可能会出现。 Specific topics to be explored include naphthalene- and anthracene-templated HDDA reactions, intra-annular HDDA reactions, “propagating HDDA reactions” for the synthesis of conjugated polymers, and the use of an iterative exponential growth strategy to produce discreet polyyne substrates designed to undergo long sequences of “domino HDDA reactions” leading to oligomeric linear多聚糖。 Hoye教授颁发了主要的教学奖项，以表彰他对本科和研究生级别的学生教育的职业生涯的承诺。该项目支持的更广泛的活动将使多个级别的化学研究专业的学生受益。科学的进步有可能通过材料科学家开辟新的追求途径，这些材料科学家在发光二极管，光伏和太阳能电池的环境中使用有机电子和光子化合物，这些应用具有巨大的社会影响潜力。这项奖项通过评估了NSF的法规效果，并通过评估了Intellitia the Intellitia the Internitia infortial and Foundit and Founditial的支持。