Mechanism and Discovery of Metal-Catalyzed Fluoroalkylation Reactions

金属催化氟烷基化反应的机理和发现

• 批准号: 1955635
• 负责人: John Hartwig
• 金额: $ 71万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-05-01 至 2024-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955635&HistoricalAwards=false
• 关键词: Mechanism; Discovery; Metal; Catalyzed; Fluoroalkylation

The Chemical Catalysis Program of the Chemistry Division supports the project by Professor John F. Hartwig in the Department of Chemistry at the University of California, Berkeley to improve catalytic processes that form organic molecules containing fluorine atoms. These studies are important because fluorinated organic molecules are vital to material, agricultural, and medicinal sciences. For example, over 30% of new pharmaceuticals and 25% of licensed herbicides contain fluorine. This project answers a series of questions to understand how these catalytic systems work. This knowledge is then being used to design solutions to overcome catalytic bottlenecks that will increase the availability of fluorinated organic molecules. The program also includes outreach activities for K-12 students on chemical catalysis topics, short training courses for the chemical workforce, and presentations to general audiences to reach future scientists from underrepresented groups.Although a large fraction of pharmaceuticals and agrochemicals contain fluorine, available fluorinated molecules are largely limited to those derived from simple fluoroarenes, trifluoromethylarenes, or trifluoroacetates. In order to reliably synthesize molecules with fluoroalkyl groups, new ways to induce and control the reactivity of fluoroalkyl transition-metal complexes in catalytic processes are needed. These studies are improving catalytic capabilities for forming fluorinated organic compounds by preparing fluoroalkyl complexes of palladium and fluoroallylic complexes of iridium and determining the factors that promote carbon-carbon bond formation with these intermediates. This fundamental work is revealing how to turnover catalytic processes involving these transition metal intermediates to advance the synthesis of fluorinated organic molecules. In addition, these studies are determining how to control the formation of stereogenic centers and how to tolerate a larger array of functional groups. This project is impacting the catalytic synthesis of molecules that are important in materials science, medicinal chemistry, and agroscience. Simultaneously, this program is providing training for a diverse group of graduate and undergraduate students, as well as outreach activities to K-12 students to motivate the next generation of scientists.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.

化学部的化学催化计划支持加利福尼亚大学伯克利分校化学系教授约翰·F·哈特维格（John F.这些研究很重要，因为氟化有机分子对于物质，农业和药物科学至关重要。例如，超过30％的新药和25％的许可除草剂含有氟。该项目回答了一系列问题，以了解这些催化系统如何工作。然后，这些知识被用于设计解决方案以克服催化瓶颈，以增加氟化有机分子的可用性。该计划还包括针对K-12学生的化学催化主题，化学劳动力的简短培训课程以及向一般受众介绍的宣传活动，以吸引来自代表性不足的群体的未来科学家。尽管很大一部分药物和硬化学含有液化分子，这些药物含有这些简单的燃料，这些分子属于这些造成的液化菌群，这些分子属于这些造成的液化剂，这些分子属于这些造成的液化剂，这些药物属于这些象征。三氟乙酸。为了可靠地与氟烷基合成分子，需要在催化过程中诱导和控制氟烷基过渡金属复合物的反应性的新方法。这些研究通过制备钯金和铱的氟烷基复合物来改善形成氟的有机化合物的催化能力，并确定用这些中间体促进碳碳键形成的因素。这项基本工作揭示了如何涉及这些过渡金属中间体的催化过程，以推动氟化有机分子的合成。此外，这些研究正在确定如何控制立体中心的形成以及如何忍受较大的官能团体。该项目正在影响在材料科学，药物化学和农业科学中重要的分子的催化合成。同时，该计划正在为多样化的研究生和本科生提供培训，并向K-12学生提供宣传活动，以激励下一代科学家。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的影响审查标准来通过评估来支持的。

项目成果

gem-Difluoroallylation of Aryl Halides and Pseudo Halides with Difluoroallylboron Reagents in High Regioselectivity

高区域选择性二氟烯丙基硼试剂对芳基卤化物和拟卤化物进行偕二氟烯丙基化

• DOI: 10.1002/anie.202111476
• 发表时间: 2021
• 期刊: Angewandte Chemie
• 作者: Sakamoto, Shu;Butcher, Trevor W.;Yang, Jonathan L.;Hartwig, John F.
• 通讯作者: Hartwig, John F.