Collaborative Research: NSF-DFG: CAS: Electrochemical Hydrogenation of Amides and Esters

合作研究：NSF-DFG：CAS：酰胺和酯的电化学氢化

• 批准号: 2140205
• 负责人: Alexander Miller
• 金额: $ 17.25万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-01-01 至 2024-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2140205&HistoricalAwards=false
• 关键词: Collaborative; Research; NSF; DFG; CAS

With funding from the National Science Foundation Division of Chemistry, Nilay Hazari from Yale University and Alex Miller from the University of North Carolina, in collaboration with the University of Göttingen in Germany, aim to develop new methods for the preparation of chemical precursors to pharmaceuticals and polymers. The project will provide fundamental guidelines on how to use electricity in chemical synthesis, leading to more environmentally friendly routes to industrial chemicals relative to current methods that rely on toxic or environmentally damaging chemicals. Students will learn new techniques and broaden their education through an international exchange program in which graduate students from the University of Göttingen will travel to either Yale or the University of North Carolina-Chapel Hill, and students from the American institutions will travel to the University of Göttingen. The hydrogenation of carboxylic acid derivatives, such as esters and amides, represents an atom economical process for the production of synthetically valuable alcohols and amines. Recent advances in hydrogenation for amine and alcohol synthesis have relied on dihydrogen gas, which is however currently produced in an environmentally harmful process from fossil fuels. In this project, a collaborative team consisting of Nilay Hazari from Yale University and Alex Miller from the University of North Carolina-Chapel Hill, in further collaboration with the University of Göttingen, will use funding from the National Science Foundation Division of Chemistry to develop electrocatalysts for the reduction of esters and amides using protons and electrons. The approach will leverage detailed mechanistic studies on a recently developed manganese electrocatalyst for ketone reduction, including kinetic analysis and spectro-electrochemical detection of intermediates, to provide a basis for developing systems capable of reducing esters and amides. A particular focus will be on synthesizing key hydride intermediates and establishing their thermodynamic and kinetic hydricity. In addition to promising more sustainable synthetic methods, electrochemical hydrogenation may well emerge as a hydrogenation method that is more tolerant of functional groups, such as acidic sites, and, as such, find broad application in academia and industry.This research was funded under the NSF-DFG Lead Agency Activity in Electrosynthesis and Electrocatalysis (NSF-DFG EChem) opportunity NSF 20-578.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.

在国家科学基金会化学部的资助下，耶鲁大学的尼拉·哈扎里（Nilay Hazari）和北卡罗来纳大学的亚历克斯·米勒（Alex Miller）与德国戈丁根大学合作，旨在开发新方法，以为药物和聚合物制备化学先驱者。该项目将提供有关如何在化学合成中使用电力的基本准则，从而导致相对于依赖有毒或环境破坏化学物质的当前方法，通往工业化学物质的途径更加环保。学生将通过一项国际交流计划学习新技术并扩大他们的教育，在该计划中，来自哥廷根大学的研究生将前往耶鲁大学或北卡罗来纳大学 - chapel山，而美国机构的学生将前往戈丁根大学。羧酸衍生物（例如酯和酰胺）的氢化代表了生产合成有价值的醇和胺的原子经济过程。胺和酒精合成的氢化的最新进展依赖于二氢气体，但是，二氢气体目前是从化石燃料的环境有害过程中产生的。在这个项目中，由耶鲁大学的Nilay Hazari和北卡罗来纳大学 - 教堂山山的Alex Miller组成的合作团队将与Göttingen大学进一步合作，将使用国家科学基金会化学基金会的资金来开发电催化剂，以减少使用Protons and Electons和Electeron和电气的电气降低酯和磁性的电力。该方法将利用最近开发的锰电催化剂来减少酮的详细机械研究，包括动力学分析和中间体的光谱电化学检测，为开发能够减少酯和酰胺的系统提供基础。特别的重点将是合成关键的水力基中间体并确定其热力学和动力学水性。除了承诺更可持续的合成方法外，电化学氢化还可以很好地成为一种氢化方法，它更容忍了官能团，例如酸性站点，因此在学术界和行业中找到了广泛的应用。这项研究是在NSF-DFG铅中的20-20-20-echem seem sechsissipy（N.NS.N.NS.N.THS）中资助的，奖项反映了NSF的法定任务，并通过使用基金会的知识分子优点和更广泛的影响审查标准评估被认为是宝贵的支持。