Efficient and Mild Synthesis of Arynes from Readily Available Building Blocks

在化学系化学合成项目的支持下，波特兰州立大学的David Stuart和他的团队正在研究涉及芳香环的新化学反应的发展。由于芳香环是用于医学、农业和技术的分子的重要组成部分，因此发现将芳香环结合到分子中的新方法将有助于推进这些具有重要社会意义的领域。这项工作将专门针对芳香烃的使用；也就是含有三键的芳香环。Arynes有一个非常活泼的三键，可以进行常规芳香体系不能进行的反应。这项工作将重点关注的两个重要领域是：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相关的浪费；2)使用比目前使用的更温和的条件来生成芳烃。除了对学术界和工业界的科学效益外，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STEM（科学、技术、工程和数学）职业所需的知识和技能的正规教育。此外，外展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。芳烃是一种高活性的合成中间体，具有与母体芳烃不同的反应谱。这一特性使得芳香烃对于在药品、农用化学品和其他合成材料中发现的芳香环的多样化非常有用。然而，获得arynes仍然是有效的或温和的，但不是两者兼而有之。根据该奖项，Stuart小组的目标是开发新的化学反应，从简单和广泛可用的化学构建块中获得芳烃，使用温和的条件来扩大芳烃的官能团相容性。关键的创新是使用“onium”离开基团，这些基团将被安装在原位，作为更具反应性的炔前体。具体来说，该团队将使用带正电的硫（磺胺）和碘（碘）离去基来实现这些转化。这项研究的预期结果是，合成化学家将有能力以以前不可能的方式扩大芳烃的化学空间。该奖项反映了美国国家科学基金会的法定使命，并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，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.