RUI: Phosphorus-Directed C-H Borylation and Reactivity of Phosphaboronates

RUI：磷定向的 C-H 硼化和磷酸硼酸盐的反应性

• 批准号: 2154645
• 负责人: Timothy Clark
• 金额: $ 30万
• 依托单位: University of San Diego
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154645&HistoricalAwards=false
• 关键词: RUI; Phosphorus; Directed; Borylation; Reactivity

With the support of the Chemical Catalysis Program in the Division of Chemistry, Professor Timothy Clark of the University of San Diego is studying transition metal-catalyzed processes that enable the selective introduction of boron into organic molecules that contain phosphorus. Subsequent reactions that allow for replacement of the boron residue with yet other groups of ultimate interest are also under investigation with the net aim of achieving the manufacture of value-added organophosphorus products. These endeavors are significant because of the fundamental advances to borylation and boron-conversion chemistry that are anticipated and due to the importance of the kinds of organophosphorus products being generated, which have potential applications as pharmaceutical agents, agrochemicals, and other advanced materials of broad utility. Professor Clark works primarily with undergraduate student coworkers at the University of San Diego and, accordingly, the broader impacts of the funded project will extend to the education and training of young people in STEM (science, technology, engineering and mathematics) fields. In addition, a post-doctoral associate working on the project will receive mentoring from the PI to build toward a future career in research and teaching thus further enriching the pool of human resources in science and education.The funded research is focused on significantly expanding recent advances in C–H borylation chemistry to enable efficient new routes to valuable chiral phosphines and phosphonates. Two distinct aims are being pursued that explore this theme in the context of either alkyl or aryl organophosphorus compounds. In Aim 1, iridium-catalyzed C(sp3)–H borylation of alkyl phosphines, phosphonates, and related organophosphorus species, is being investigated in the presence of chiral ligands to achieve an enantioselective synthesis of secondary alkyl boronates. Sequencing this chemistry with the expansive range of reactions that allow for the stereospecific conversion of C–B bonds into C–C or C–X (X = O, N) bonds allows for expedient syntheses of useful enantioenriched chiral phosphines. In Aim 2, biaryl formation from aryl boronates generated by phosphorus-directed ortho borylation of aryl phosphonates, is being explored via novel oxidative copper-catalyzed homo- and hetero-coupling processes. Opportunities for executing this chemistry, which offers a concise route to some important classes of axially chiral bisphosphine ligands, in an enantioselective modality are also under investigation.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.

在化学系化学催化项目的支持下，圣地亚哥大学的Timothy Clark教授正在研究过渡金属催化过程，该过程能够将硼选择性地引入含有磷的有机分子中。随后的反应也在研究中，这些反应允许用其他最终感兴趣的基团取代硼渣，其最终目标是实现制造增值有机磷产品。这些努力是重要的，因为预期在硼化和硼转化化学方面取得了根本性的进展，也因为所产生的各种有机磷产品的重要性，这些产品在制药剂、农用化学品和其他用途广泛的先进材料方面具有潜在的应用。克拉克教授主要与圣地亚哥大学的本科生同事合作，因此，资助项目的更广泛影响将扩展到STEM（科学、技术、工程和数学）领域的年轻人的教育和培训。此外，一名参与该项目的博士后将得到PI的指导，以建立未来的研究和教学事业，从而进一步丰富科学和教育方面的人力资源。该资助研究的重点是显著扩展C-H硼化化学的最新进展，为有价值的手性膦和膦酸盐提供有效的新途径。在烷基或芳基有机磷化合物的背景下，正在追求探索这一主题的两个不同目标。在Aim 1中，在手性配体存在的情况下，研究了铱催化的烷基膦、膦酸盐和相关有机磷物种的C(sp3) -H硼化反应，以实现仲烷基硼酸盐的对映选择性合成。利用广泛的反应范围对这种化学进行排序，使C-B键立体特异性转化为C-C或C-X （X = O， N）键，可以方便地合成有用的富集对映体的手性膦。在Aim 2中，通过新的氧化铜催化的同质偶联和异质偶联过程，探索由磷酸芳基邻位硼酸芳基生成联芳基。这种化学反应为一些重要的轴手性双膦配体提供了一条简明的途径，以对映选择性的方式进行化学反应的机会也在研究中。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。