Palladium-Catalyzed Aerobic Allylic Oxidations: Mechanisms and Applications

钯催化的有氧烯丙基氧化：机制和应用

• 批准号: 1953926
• 负责人: Shannon Stahl
• 金额: $ 49万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-06-01 至 2023-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1953926&HistoricalAwards=false
• 关键词: Palladium; Catalyzed; Aerobic; Allylic; Oxidations

With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Shannon Stahl to design agents that speed chemical reactions (catalysts) to perform specific chemical transformations (oxidize organic molecules with oxygen). Oxidation processes are important chemical reactions for the production of commodity chemicals, pharmaceuticals, and agrochemicals. Unfortunately, chemical oxidations usually use reagents (oxidants) that are toxic, are more powerful than needed and result in a large number of unwanted by-products, and/or generate waste that is harmful to the environment. Professor Stahl and his group at the University of Wisconsin–Madison are developing catalysts that oxidize chemical feedstocks called alkenes with oxygen; this oxidant generates only water as a by-product. These studies address the efficiency of the catalysts, trying to make them longer-lasting and more selective. This research program trains graduate and undergraduate students to become part of the chemical workforce and to recruit underrepresented minorities to STEM disciplines. In addition, important safety protocols are being designed to work with oxygen and organic molecules on large scale and thus, this research has important industrial relevance.The selective oxidation of C–H bonds is a key challenge in chemical synthesis and in the chemical industry, as it enables more efficient synthesis of novel and known chemical structures. Professor Stahl and his group are developing and characterizing palladium catalysts that mediate selective oxidation of allylic C–H bonds using molecular oxygen as the terminal oxidant. The resulting allylic carboxylate products are versatile intermediates in numerous synthetically-useful, secondary functionalization reactions. Research efforts explore strategies to enhance the stability of the Pd catalysts as a means of achieving high turnover numbers. Approaches towards this goal include the design of new ligands and the identification of reaction conditions that enable the catalysts to have intrinsic thermodynamic stability. Mechanistic studies play an important role in this effort, aided by innovative mechanistic tools such as a high-pressure NMR reactor capable of continuous on-line delivery of O2 and gas-uptake kinetic analysis. These fundamental studies focused on the achievement of practical goals, and the concomitant development of important safety protocols, provides a strong training environment for a diverse group of graduate and undergraduate students.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.

有了这个奖项，NSF化学部的化学催化计划正在支持Shannon斯塔尔教授的研究，以设计加速化学反应（催化剂）的试剂来执行特定的化学转化（用氧气氧化有机分子）。氧化过程是生产日用化学品、药物和农用化学品的重要化学反应。不幸的是，化学氧化通常使用有毒的试剂（氧化剂），比所需的更强大，并导致大量不需要的副产物，和/或产生对环境有害的废物。威斯康星大学麦迪逊分校的斯塔尔教授和他的小组正在开发催化剂，用氧气氧化称为烯烃的化学原料;这种氧化剂只产生水作为副产品。这些研究解决了催化剂的效率，试图使它们更持久，更有选择性。该研究计划培养研究生和本科生成为化学劳动力的一部分，并招募代表性不足的少数民族STEM学科。此外，重要的安全协议正在设计中，以大规模使用氧气和有机分子，因此，这项研究具有重要的工业意义。C-H键的选择性氧化是化学合成和化学工业中的关键挑战，因为它可以更有效地合成新的和已知的化学结构。斯塔尔教授和他的小组正在开发和表征钯催化剂，该催化剂使用分子氧作为末端氧化剂介导烯丙基C-H键的选择性氧化。所得烯丙基羧酸酯产物是许多合成上有用的二次官能化反应中的通用中间体。研究工作探索提高Pd催化剂稳定性的策略，作为实现高周转数的手段。实现这一目标的方法包括设计新的配体和确定反应条件，使催化剂具有固有的热力学稳定性。机械研究在这方面发挥了重要作用，通过创新的机械工具，如高压NMR反应器能够连续在线提供O2和气体吸收动力学分析的帮助。这些基础研究侧重于实际目标的实现，以及重要安全协议的同步发展，为多样化的研究生和本科生群体提供了强大的培训环境。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Ethylene oligomerization into linear olefins over cobalt oxide on carbon catalyst

氧化钴碳催化剂上乙烯齐聚成直链烯烃

• DOI: 10.1039/d1cy00207d
• 发表时间: 2021
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: Jonathan, Alvin;Eagan, Nathaniel M.;Bruns, David L.;Stahl, Shannon S.;Lanci, Michael P.;Dumesic, James A.;Huber, George W.
• 通讯作者: Huber, George W.

Multichannel gas-uptake/evolution reactor for monitoring liquid-phase chemical reactions

用于监测液相化学反应的多通道气体吸收/放出反应器

• DOI: 10.1063/5.0043007
• 发表时间: 2021
• 期刊: Review of Scientific Instruments
• 影响因子: 1.6
• 作者: Salazar, Chase A.;Thompson, Blaise J.;Knapp, Spring M. M.;Myers, Steven R.;Stahl, Shannon S.
• 通讯作者: Stahl, Shannon S.