Electrocatalytic Oxidation of Alcohols, Amines, and Carbon-Carbon Bonds

醇、胺和碳-碳键的电催化氧化

• 批准号: 1762350
• 负责人: William Jones
• 金额: $ 45.4万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1762350&HistoricalAwards=false
• 关键词: Electrocatalytic; Oxidation; Alcohols; Amines; Carbon

With funding from the Chemical Catalysis Program of the Division of Chemistry, Dr. William D. Jones of the University of Rochester is developing new catalytic materials capable of removing hydrogen from organic molecules to make more valuable products. In this new method, hydrogen is transferred from the organic molecule to a carrier molecule using a metal catalyst. The carrier molecules are then recycled many times. Dr. Jones is studying the individual steps of the reaction cycle. These catalytic reactions have applications in the synthesis of pharmaceuticals and may also provide a better understanding of how electrical energy from hydropower or wind turbines could be captured and stored for later use on demand. Dr. Jones is engaged in outreach activities to inform the public about novel new concepts for energy storage and organic compound synthesis. He and his group participate in public radio shows such as WXXI Connections, and speak on television news programs. The researchers include both undergraduate and graduate students who are being trained to solve difficult technical problems of broad societal interest. This research advances the national health and prosperity by contributing to technical innovations in the pharmaceuticals and renewable energy industries. Dr. Jones is developing homogeneous transition metal catalysts that can be used to dehydrogenate alcohols, amines, and heterocycles electrochemically. The group is studying the use of new and known catalysts in combination with quinones as electron transfer mediators, as the latter have the ability to undergo reversible electrochemical reduction and oxidation, and show promise as mediators with transition metal catalysts. The group is examining stoichiometric reactions for alcohol and amine dehydrogenation with various quinones as hydrogen acceptors. The group is also developing electrochemical recycling of the hydroquinone hydrogen acceptors. By proper choice of solvent and electrolyte, an electrochemical route for dehydrogenations is being extended to substrates that can produce heterocycles such as indoles and quinolones. Finally, this electrochemical method is being used in applications for dehydrogenation of activated C-C bonds to generate oxidized organic products that serve as building blocks in the chemical and pharmaceutical industry. This work has the potential to occur with dihydrogen as the only byproduct, using electrochemistry to provide the driving force for the thermodynamically uphill reaction. This work is focusing on the use of these catalysts in organic synthesis, but also can find applications in hydrogen storage, and fuel cells. The students engaged in this research are learning advanced techniques for handling sensitive compounds and therefore are being trained as Highly Qualified Personnel (HQP) for work in advanced industrial research labs.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资助下，罗彻斯特大学的William D. Jones博士正在开发新的催化材料，能够从有机分子中去除氢，从而生产出更有价值的产品。在这种新方法中，氢通过金属催化剂从有机分子转移到载体分子。然后，载体分子被循环利用很多次。琼斯博士正在研究反应循环的各个步骤。这些催化反应在药物合成中有应用，也可能使人们更好地了解如何捕获和储存来自水力或风力涡轮机的电能以供以后需要时使用。琼斯博士从事外展活动，向公众介绍能源储存和有机化合物合成的新概念。他和他的团队参加公共广播节目，如WXXI Connections，并在电视新闻节目中发言。研究人员包括本科生和研究生，他们正在接受培训，以解决具有广泛社会利益的困难技术问题。这项研究通过促进制药和可再生能源行业的技术创新，促进了国家的健康和繁荣。琼斯博士正在开发均相过渡金属催化剂，可用于电化学脱氢醇、胺和杂环。该小组正在研究将新的和已知的催化剂与醌结合作为电子转移介质的使用，因为后者具有进行可逆电化学还原和氧化的能力，并且与过渡金属催化剂结合作为介质有希望。该小组正在研究以各种醌作为氢受体的醇和胺脱氢的化学计量反应。该小组还在开发对苯二酚氢受体的电化学回收。通过适当选择溶剂和电解质，电化学脱氢的途径正在扩展到可以产生杂环化合物的底物，如吲哚和喹诺酮类。最后，这种电化学方法被用于活化C-C键的脱氢，以产生氧化的有机产品，作为化学和制药工业的基石。这项工作有可能以二氢作为唯一的副产物，利用电化学为热力学上坡反应提供驱动力。这项工作的重点是在有机合成中使用这些催化剂，但也可以在储氢和燃料电池中找到应用。参与这项研究的学生正在学习处理敏感化合物的先进技术，因此正在被培训为高级工业研究实验室工作的高素质人才（HQP）。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。

项目成果

The functionalization of benzene by boranes using trispyrazolylborate complexes

使用三吡唑基硼酸酯配合物通过硼烷对苯进行官能化

• DOI: 10.1016/j.poly.2021.115042
• 发表时间: 2021
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Vetter, Andrew J.;DiBenedetto, Tarah A.;Ritz, Mikhaila D.;Jones, William D.
• 通讯作者: Jones, William D.

Bisoxazoline-pincer ligated cobalt-catalyzed hydrogenation of alkenes

• DOI: 10.1016/j.poly.2020.114416
• 发表时间: 2020-04
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Mikhaila D. Ritz;A. M. Parsons;Philip N Palermo;W. Jones

Synthesis, characterization, and structure determination of Cp*Ir(dpms)Cl

Cp*Ir(dpms)Cl 的合成、表征和结构测定

• DOI: 10.1016/j.ica.2022.121210
• 发表时间: 2022
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Pohorenec, Ryan;Drelles, William G.;Cuneo, Daniel;Brennessel, William W.;Jones, William D.
• 通讯作者: Jones, William D.

Iron‐Catalyzed Dehydrogenation of Alcohols Using Benzoquinones as Electrochemically Regenerable Mediators

使用苯醌作为电化学可再生介体铁催化醇脱氢

• DOI: 10.1002/ejoc.202200149
• 发表时间: 2022
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: Ritz, Mikhaila D.;Jones, William D.
• 通讯作者: Jones, William D.

Reversible Concerted Metalation–Deprotonation C–H Bond Activation by [Cp*RhCl 2 ] 2

[Cp*RhCl 2 ] 2 可逆协同金属化 - 去质子化 C - H 键激活

• DOI: 10.1021/acs.joc.9b01716
• 发表时间: 2019
• 期刊: The Journal of Organic Chemistry
• 作者: VanderWeide, Andrew I.;Brennessel, William W.;Jones, William D.
• 通讯作者: Jones, William D.