RUI: Mechanisms of C-F and S-F Bond Activation and Cross-coupling with Bidentate N-heterocyclic Carbene Nickel Catalysts

RUI：双齿N-杂环卡宾镍催化剂的C-F和S-F键活化及交叉偶联机理

• 批准号: 2350537
• 负责人: Sabine Chantal Stieber
• 金额: $ 29.79万
• 依托单位: Cal Poly Pomona Foundation, Inc.
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-09-01 至 2027-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2350537&HistoricalAwards=false
• 关键词: RUI; Mechanisms; Bond; Activation; Cross

In this RUI project, with support from the Chemical Structure, Dynamics & Mechanisms-B Program of the Chemistry Division, S. Chantal E. Stieber of the Department of Chemistry at California State Polytechnic University, Pomona is studying earth-abundant nickel catalysts for installing fluorine onto molecules with potential for future use in imaging and pharmaceuticals. The goal of this work is to determine how the structure of the nickel catalyst affects the reactivity with carbon-fluorine and sulfur-fluorine bonds, and the resulting catalytic performance. This work involves advanced organometallic, organic, and inorganic research training for students at a primarily undergraduate institution. This grant will additionally support paid summer research training positions, development of new research tutorial videos, and hosting diverse seminar speakers. Combined, these efforts will broaden participation in science and provide workforce training at an under-resourced Hispanic-serving institution. Nickel systems for carbon-fluorine and sulfur-fluorine activation are not widely explored, but have the potential to provide new routes for installing fluorine on molecules for 19F labeling, silylation, and borylation. This work will probe the fundamental reactivity of nickel toward carbon-fluorine and sulfur-fluorine bonds in aryl fluorides and sulfonyl fluorides as a function of the ligand environment and resulting effects on cross-coupling reactions. A series of bidentate N-heterocyclic carbene (NHC) nickel complexes will be synthesized to answer the following questions: (i) How do the ligand and the substrate affect cis- versus trans-oxidative addition of carbon-fluorine or sulfur-fluorine bonds at nickel? (ii) Does cis- versus trans-oxidative addition of carbon-fluorine and sulfur-fluorine bonds at nickel affect cross-coupling reactivity for silylation and borylation catalysis? and (iii) How does nickel react with sulfonyl fluorides as compared to aryl fluorides? These studies are expected to provide fundamental information on the structural features that confer maximal reactivity on Ni-NHC complexes for C-F and S-F bond activation.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.

在这个RUI项目中，在化学结构，动力学和机制B计划的支持下，加利福尼亚州立理工大学化学系的S. Chantal E. Stieber，Pomona正在研究地球丰富的镍催化剂，用于将氟催化剂安装到分子上，并有可能在成像和制药中使用未来使用。这项工作的目的是确定镍催化剂的结构如何影响碳氟和硫氟纤维键的反应性，以及所得的催化性能。这项工作涉及主要是本科机构的学生的高级有机金属，有机和无机研究培训。该赠款还将支持有偿的夏季研究培训职位，开发新的研究教程视频以及主持不同的研讨会演讲者。这些努力结合在一起，将扩大对科学的参与，并在资源不足的西班牙裔服务机构中提供劳动力培训。 未广泛探索用于碳氟氟和硫氟激活的镍系统，而是有潜力提供新的途径，以在分子上安装氟以进行19F标记，硅烷二烯二烯和体内化。这项工作将探测镍对芳基氟化物和磺酰基氟化物中碳氟和硫氟键的基本反应性，这是配体环境的函数，以及对交叉偶联反应的影响。将合成一系列二态N-杂环碳纤维（NHC）镍配合物来回答以下问题：（i）镍和底物如何影响镍含碳或氧化的碳氟氟或硫氟氟氟氟荷兰键与镍的氧化添加？ （ii）在镍处的碳氟氟和硫氟糖键是否会影响交叉偶联反应性，以使其硅烷化和气体化催化反应性吗？ （iii）与芳基氟化物相比，镍与磺酰基氟化物有何反应？ 预计这些研究将提供有关结构特征的基本信息，这些特征赋予C-F和S-F键激活的Ni-NHC复合物的最大反应性。该奖项反映了NSF的法定任务，并被认为值得通过基金会的知识分子优点和更广泛的影响标准通过评估来进行评估。