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和北卡罗来纳州大学的Alex米勒与德国的哥廷根大学合作，旨在开发制备药物和聚合物化学前体的新方法。该项目将提供关于如何在化学合成中使用电力的基本指导方针，从而使工业化学品的生产路线相对于目前依赖有毒或破坏环境的化学品的方法更加环保。学生将通过国际交流计划学习新技术并扩大他们的教育，其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教堂山分校，来自美国机构的学生将前往哥廷根大学。羧酸衍生物如酯和酰胺的氢化代表了用于生产合成有价值的醇和胺的原子经济方法。用于胺和醇合成的氢化的最新进展依赖于二氢气体，然而，二氢气体目前是在对环境有害的过程中由化石燃料产生的。在该项目中，由耶鲁大学的Nilay Hazari和北卡罗来纳大学教堂山分校的Alex米勒组成的合作团队与哥廷根大学进一步合作，将利用国家科学基金会化学部的资金开发用于使用质子和电子还原酯和酰胺的电催化剂。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，包括中间体的动力学分析和光谱电化学检测，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，并建立其热力学和动力学的hydricity。除了有希望的更可持续的合成方法之外，电化学氢化很可能作为一种氢化方法出现，该方法对官能团如酸性位点更耐受，并且因此，在学术界和工业界找到了广泛的应用。这项研究得到了NSF-DFG电合成和电催化牵头机构活动的资助（NSF-DFG ECHEM）机会NSF 20- 578.该奖项反映了NSF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.