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S.化学部化学结构、动力学机制-B项目的支持下。尚塔尔E.波莫纳加州州立理工大学化学系的Stieber正在研究地球上丰富的镍催化剂，用于将氟安装到未来可能用于成像和制药的分子上。这项工作的目标是确定镍催化剂的结构如何影响与碳-氟和硫-氟键的反应性，以及由此产生的催化性能。这项工作涉及先进的有机金属，有机和无机研究培训的学生在一个主要的本科院校。这笔赠款还将支持带薪暑期研究培训职位，开发新的研究教程视频，并举办各种研讨会演讲。结合起来，这些努力将扩大科学的参与，并在资源不足的西班牙裔服务机构提供劳动力培训。 用于碳-氟和硫-氟活化的镍系统尚未被广泛开发，但有可能为在分子上安装氟以进行19 F标记、甲硅烷基化和硼基化提供新的途径。这项工作将探讨镍对芳基氟和磺酰氟中的碳-氟和硫-氟键的基本反应性，作为配体环境的函数，并对交叉偶联反应产生影响。本文将合成一系列双齿N-杂环卡宾（NHC）镍配合物以回答以下问题：（i）配体和底物如何影响碳-氟或硫-氟键在镍上的顺式与反式氧化加成？(ii)镍上碳-氟键和硫-氟键的顺式与反式氧化加成是否会影响甲硅烷基化和硼基化催化的交叉偶联反应性？和（iii）与芳基氟化物相比，镍与磺酰氟化物如何反应？ 这些研究预计将提供基本信息的结构特征，赋予最大的反应性镍-NHC复合物的C-F和S-F键activation.This奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。