Efficient and Mild Synthesis of Arynes from Readily Available Building Blocks

从现成的结构单元高效温和地合成芳炔

• 批准号: 2247802
• 负责人: David Stuart
• 金额: $ 49.06万
• 依托单位: Portland State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247802&HistoricalAwards=false
• 关键词: Efficient; Mild; Synthesis; Arynes; Readily

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.

在化学综合计划在化学系的支持下，波特兰州立大学的戴维·斯图尔特（David Stuart）和该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，农业和技术中使用的分子的重要组成部分，因此发现将它们纳入分子中的新方法将有助于推进这些具有社会重要的领域。这项工作将专门针对Arynes的使用；即，包含三键的芳族环。 Arynes具有非常反应性的三键，并且可以在常规芳族系统不进行的反应中。这项工作将重点关注的两个重要领域是1）通过采用简单且广泛的原料化学品来减少与合成芳基相关的废物，以及2）使用米勒条件比目前使用的杂物生成Arynes。除了对学术界和行业的科学益处外，这项工作还将通过开发治疗（基于课程的本科研究经验）课程来扩大本科生的研究机会。这将有助于为学生提供STEM（科学，技术，工程和数学）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历史上在茎中被边缘化的群体的代表。Anyne是一种高度反应性的合成中间体，其反应曲线与父母芳烃不同。此功能使Arynes对于在药物，农业化学和其他合成材料中发现的芳族环的多样化有用。但是，获得Arynes仍然有效或轻度，但并非两者兼而有之。根据该奖项，Stuart集团旨在开发新的化学反应，以使用轻度条件从简单而广泛的化学构建块访问Arynes，以扩大Arynes的功能组兼容性。关键的创新是使用“ Onium”，将要安装的群体作为Arynes的反应性前体。具体而言，该团队将使用带正电的硫（磺硫）和碘（iodonium）的阳离子来实现这些转变。这项研究的预期结果是，综合化学家将等同于以前无法以前无法实现的方式扩大竞技场的化学空间。该奖项反映了NSF的法定任务，并通过使用基金会的知识分子和更广泛的影响审查标准来通过评估来诚实地通过评估来诚实地支持。