CAREER: Chemoselective Functionalization of Strong C-O, C-F and C-H Bonds Using Boron Chemistry

职业：利用硼化学对强 C-O、C-F 和 C-H 键进行化学选择性功能化

• 批准号: 2239556
• 负责人: Florence Williams
• 金额: $ 65万
• 依托单位: University of Iowa
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-01 至 2028-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2239556&HistoricalAwards=false
• 关键词: CAREER; Chemoselective; Functionalization; Strong; Bonds

With the support of the Chemical Synthesis Program in the Division of Chemistry and the Established Program to Stimulate Competitive Research (EPSCoR), Florence Williams of the University of Iowa is studying the ability of simple boron-containing reagents to deconstruct chemical compounds in useful ways to create value-added materials and/or to tackle contemporary environmental challenges. The research focuses on cleavage of chemical bonds that are ubiquitous in types of materials commonly used in medicine, agriculture, engineering, and commerce. During the course of these transformations, the key boron reagents are themselves degraded into innocuous boric acid – a low toxicity chemical found in household products such as laundry detergent. The methodology developed will be evaluated in a variety of important contexts, including: (1) for the controlled deconstruction (depolymerization) of epoxy resin plastics, which are not currently recycled, and (2) for the breakdown of per- and poly-fluoroalkyl substances (PFAS), which have arisen as persistent pollutants that cause significant health concerns. In addition to offering anticipated technological advancements in the areas of plastics recycling and PFAS remediation, the broader impacts of the funded project extend to the benefits accrued to society as Dr. Williams and her coworkers engage in a variety of activities to improve access to chemical education and to enhance the diversity, equity, and inclusion landscape at the University of Iowa. For example, continued development of a widely available smart phone-based app to facilitate undergraduate student learning in introductory organic chemistry courses is in progress and Dr. Williams is spearheading the creation of an American Chemical Society Women Chemist's Committee (ACS WCC) chapter at her institution. Taken together, these initiatives are anticipated to make the science of chemistry more accessible and inclusive to a diverse population of students and to increase general engagement in important organic chemistry-related topics.Under this award, the Williams team at the University of Iowa will focus on the development of boron-mediated reactions for the functionalization of traditionally inert C–O, C¬–F, and C–H bonds and the demonstration and evaluation of these processes in complex molecular settings. The work builds on insights gained from earlier findings of the Williams laboratory which revealed the tunability of boron trihalide-mediated C–F and C–O bond cleavage reactions and successful application of the latter to lignocellulose polymer separation. New research is designed to expand understanding of the key parameters driving chemoselectivity in both C–F and C–O cleavage contexts, to explore novel (radical-based) mechanisms of reactivity that expand into C–H functionalization, and to evaluate the potential of these reactions for the aforementioned degradation of PFAS and epoxy resin plastics. A design of experiments (DoE) approach will be employed to reveal mechanistic and operational nuances not previously appreciated for the chemo- and regio-selective cleavage of ethereal bonds. Finally, it is noted that undergraduate and graduate students working on the funded project will receive educational and experimental training preparing them to make significant future contributions to the Nation's STEM (science, technology, engineering and mathematics) workforce.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.

在化学合成计划的支持下，在化学和启发竞争研究的既定计划中（EPSCOR），爱荷华大学的佛罗伦萨·威廉姆斯（Florence Williams）研究了简单的含硼试剂以有用的方式解构化学化合物的能力，以创造增值材料和/或应对当代环境挑战。该研究的重点是在医学，农业，工程和商业中常用的材料类型中无处不在的化学债券进行分裂。在这些转化过程中，关键的硼试剂本身会降解为无害的硼酸 - 一种在洗衣等家用产品中发现的低毒性化学物质。开发的方法将在各种重要环境中进行评估，包括：（1）环氧树脂塑料的受控解构（去聚合），目前尚未回收这些塑料，以及（2）对伴随着重要健康污染物持续危害的per和poly-fluoralkyl物质（PFA）的细分（PFA）。除了在塑料回收和PFA修复领域提供预期的技术进步外，该资助项目的更广泛影响延伸到社会上积累的收益，因为威廉姆斯博士和她的同事从事各种活动，以改善化学教育的机会，并增强了尤利亚大学的多样性，公平和纳入景观。例如，正在持续开发一个基于智能电话的广泛可用的应用程序，以促进有机化学课程中的本科生学习，威廉姆斯博士在她的机构中率先建立了美国化学学会女子化学家委员会（ACS WCC）分会的创建。 Taken together, these initiatives are anticipated to make the science of chemistry more Accessible and inclusive to a diversity population of students and to increase general engagement in important organic chemistry-related topics.Under this award, the Williams team at the University of Iowa will focus on the development of boron-mediated reactions for the functionalization of traditionally inert C–O, C¬–F, and C–H bonds and the demonstration and evaluation of these processes in complex molecular 设置。这项工作是基于威廉姆斯实验室早期发现获得的见解，该发现揭示了硼Trihalide介导的C – F和C – O键裂解反应以及后者在木质纤维素聚合物分离中的成功应用。新的研究旨在扩展对C – F和C型裂解环境中推动化学选择性的关键参数的理解，以探索反应性的新颖（基于基于激进的）机制，这些机制扩展为C – H功能化，并评估这些反应的潜力，这些反应的潜力是PFAS和Epoxy Resin Plastics的优先降解。将采用实验方法（DOE）方法的设计，以揭示以前对空灵键的化学和调节性切割裂解的机械和操作细微差别。 Finally, it is noted that undergraduate and graduate students working on the funded project will receive educational and experimental training preparing them to make significant future contributions to the Nation's STEM (science, technology, engineering and mathematics) workforce.This award reflects NSF's statutory mission and has been deemed honestly of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.