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

在美国国家科学基金会化学部的资助下，耶鲁大学的Nilay Hazari和北卡罗来纳大学的Alex Miller与德国Göttingen大学合作，旨在开发制备药物和聚合物化学前体的新方法。该项目将提供如何在化学合成中使用电力的基本指导方针，相对于目前依赖有毒或对环境有害的化学物质的方法，为工业化学品提供更环保的途径。学生们将通过一项国际交流计划学习新技术并拓宽他们的教育。根据该计划，Göttingen大学的研究生将前往耶鲁大学或北卡罗来纳大学教堂山分校，而美国院校的学生将前往Göttingen大学。羧酸衍生物的氢化反应，如酯和酰胺，是生产有合成价值的醇和胺的原子经济过程。最近在胺和醇合成加氢方面取得的进展依赖于二氢气，然而，二氢气目前是以一种对环境有害的方法从化石燃料中产生的。在这个项目中，一个由耶鲁大学的Nilay Hazari和北卡罗来纳大学教堂山分校的Alex Miller组成的合作团队将与Göttingen大学进一步合作，利用国家科学基金会化学部的资金开发电催化剂，用于使用质子和电子还原酯和酰胺。该方法将利用最近开发的用于酮还原的锰电催化剂的详细机理研究，包括动力学分析和中间体的光谱电化学检测，为开发能够还原酯和酰胺的系统提供基础。一个特别的重点将是合成关键的氢化物中间体和建立他们的热力学和动力学水性。除了更有前景的可持续合成方法外，电化学加氢很可能成为一种对官能团（如酸性位点）更耐受的加氢方法，并因此在学术界和工业界得到广泛应用。这项研究是由NSF- dfg牵头机构在电合成和电催化活动（NSF- dfg化学）机会NSF 20-578资助的。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。

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.