Efficient and Mild Synthesis of Arynes from Readily Available Building Blocks

在化学系化学合成计划的支持下，波特兰州立大学的大卫·斯图尔特和这个团队正在研究涉及芳香环的新化学反应的发展。由于芳环是用于医药、农业和科技的分子的重要组成部分，因此发现将芳环结合到分子中的新方法将有助于推动这些具有社会重要性的领域的发展。这项工作将专门针对芳烃的使用，即包含三个键的芳环。芳烃具有非常活泼的三键，在传统芳香体系不能进行的反应中可以进行。这项工作将侧重于两个重要领域：1)通过使用简单和广泛可用的原料化学品来减少传统上与合成芳烃有关的浪费；2)使用比目前使用的更温和的条件生产芳烃。除了给学术界和工业界带来科学上的好处外，这项工作还将通过开发CURE(基于课程的本科生研究经验)课程来扩大本科生的研究机会。它将有助于为学生提供在STEM(科学、技术、工程和数学)职业所需的知识和技能方面的正规教育。此外，外联活动将有助于扩大在STEM中历史上被边缘化的群体的代表性。芳烃是一种反应活性很高的合成中间体，其反应轮廓与母体芳烃不同。这一特点使得芳烃对药物、农用化学品和其他合成材料中发现的芳香环的多样化很有用。然而，获得芳烃的途径要么有效，要么温和，但不能两者兼而有之。根据该奖项，斯图尔特小组的目标是开发新的化学反应，利用温和的条件从简单和广泛可用的化学构件中获得芳烃，以扩大芳烃的官能团兼容性。关键的创新是使用将就地安装的“铀”离开基团作为更具反应性的芳烃前体。具体地说，该团队将使用带正电的硫(硫)和碘(碘)离开基团来实现这些转变。这项研究的预期结果是，合成化学家将具备以前所未有的方式扩大芳烃化学空间的能力。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis Program in the Division of Chemistry, David Stuart of Portland State University and this team are studying the development of new chemical reactions involving aromatic rings. Because aromatic rings are a vital part of molecules that are used in medicine, agriculture, and technology, the discovery of new methods to incorporate them into molecules will serve to advance these societally important fields. This work will specifically target the use of arynes; namely, aromatic rings that contain a triple bond. Arynes have a very reactive triple bond and can in reactions that conventional aromatic systems do not carry out. Two important areas that this work will focus on are 1) to reduce the waste traditionally associated with synthesizing arynes by employing simple and widely available feedstock chemicals, and 2) generating arynes using milder conditions than are used currently. In addition to the scientific benefits to academia and industry, this work will expand research opportunities for undergraduate students through the development of a CURE (course-based undergraduate research experiences) course. It will help to provide students with a formal education in the knowledge and skills that are needed for a career in STEM (science, technology, engineering and mathematics). Additionally, outreach activities will help expand the representation of groups that have been historically marginalized in STEM.An aryne is a highly reactive synthetic intermediate having a reaction profile that is distinct from the parent arene. This feature renders arynes useful for the diversification of aromatic rings that are found in pharmaceuticals, agrochemicals, and other synthetic materials. However, access to arynes remains either efficient or mild, but not both. Under this award, the Stuart group aims to develop new chemical reactions to access arynes from simple and widely available chemical building blocks using mild conditions to expand the functional group compatibility of arynes. The key innovation is to use “onium” leaving groups that are to be installed in situ as more reactive precursors to arynes. Specifically, the team will use positively charged sulfur (sulfonium) and iodine (iodonium) leaving groups to achieve these transformations. The anticipated outcome of this research is that synthetic chemists will be equipped to expand the chemical space of arenes in ways not previously possible.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.