CAS: Tuning Deoxyfluorination Reactivity and Selectivity by Coherently Modulating Fluoride-pi Interaction Strength, SNAr Kinetics, and Leaving Group Ability

CAS：通过连贯调节氟化物-π 相互作用强度、SNAr 动力学和离去基团能力来调节脱氧氟化反应性和选择性

• 批准号: 2247635
• 负责人: Haoran Sun
• 金额: $ 51.28万
• 依托单位: University of South Dakota Main Campus
• 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=2247635&HistoricalAwards=false
• 关键词: CAS; Tuning; Deoxyfluorination; Reactivity; Selectivity

With support of the Chemical Structure, Dynamics & Mechanisms-B program of the Chemistry Division, Professor Haoran Sun of the Department of Chemistry at University of South Dakota is developing next-generation fluorinating reagents that are effective, safe, and economical for the preparation of a broader spectrum of organofluorine compounds of medicinal and material interests. The ultimate goal of this project is to find replacement for dangerous and expensive fluorinating reagents, which will reduce hazardous and environmental safety concerns. The complex nature and multifaceted approaches of this project provide excellent training to postdocs, graduate and undergraduate students for solving challenging problems important to today’s and tomorrow’s societal needs. Involvement of Native American community college students through both workshops and summer research not only attracts underrepresented minority group to STEM, but also helps communicate general science and technology information to their community, which will impact their economic development and wellbeing. Rational design and systematical realization of new fluorinating reagents with tunable reactivity and selectivity for a broader range of substrates remain a significant challenge in organofluorine chemistry. Under this project, Professor Haoran Sun's research group aims to: 1) design and prepare an array of fluorinating reagents with tunable reactivity and selectivity for deoxyfluorination of carboxylic acids, ketones, aldehydes, alcohols, phenols, and epoxides by combining different electron-deficient fluoroaromatics and fluoride salts; 2) understand how the degree of electron-deficiency of these fluoroaromatics affects deoxyfluorination through modulation of fluoride-pi interaction strength, kinetics of the fluoride nucleophilic attack in the rate-determining step, and corresponding leaving group ability; 3) advance fundamental understanding of the correlation between key structure-property factors: molecular electron-deficiency (pi-acidity) scale, fluoride-pi interaction strength, nucleophilic substitution reactivity, leaving group ability, and overall deoxyfluorination reactivity and selectivity; and 4) train students to solve challenging chemistry problems with multifaceted systematic approaches including synthetic, physical organic, and computational chemistries. The results from this project has the potential to provide fundamental chemistry knowledge to other areas of research where ionic species are involved, such as catalysis, energy storage materials, ion transport in biological systems, separation, and sensing.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.

在化学司的化学结构，动力学和机制-B计划的支持下，南达科他大学化学系的Haoran Sun教授正在开发下一代荧光试剂，这些试剂有效，安全且经济，以制备更广泛的药物和材料利益的有机氟氨酸化合物。该项目的最终目的是找到替代危险且昂贵的荧光试剂，通过研讨会和夏季研究涉及美国原住民社区大学生的参与，不仅吸引了代表性不足的少数族裔群体来启动STEM，而且还可以帮助交流。一般的科学和技术信息向其社区，这将影响他们的经济发展和福祉。具有可调反应性和选择性的新型荧光试剂对更广泛的底物的合理设计和系统实现仍然是有机氟化化学的重大挑战。在该项目下，海兰·孙教授的研究小组的目标是：1）设计和准备一系列具有可调反应性和选择性的荧光试剂，以脱氧氟化的脱氧氟化，3）提前了解这些荧光性的电子缺乏程度率确定的步骤和相应的离开组能力； 3）提前了解关键结构特性因素之间的相关性：分子电子缺陷（Pi-Acipity）尺度，氟化物 - PI相互作用强度，核代替反应性，离开组能力以及总体去氧化氟化反应性和选择性； 4）培训学生以多方面的系统方法（包括合成，物理组织和计算化学方法）来解决挑战化学问题。该项目的结果有可能向涉及离子物种的其他研究领域提供基本的化学知识，例如催化剂，能源存储材料，生物系统中的离子运输，分离和敏感性。这一奖项反映了NSF的法定任务，并通过基金会的知识绩效和广泛的影响来评估NSF的法定任务，并被认为是宝贵的支持。