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，耶鲁大学的尼莱·哈扎里和北卡罗来纳大学的亚历克斯·米勒与德国哥廷根大学合作，旨在开发制备药物和聚合物的化学前体的新方法。该项目将提供有关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破坏环境的化学品的方法，该项目将导致更环保的工业化学品路线。学生们将通过一个国际交换项目学习新技术，并扩大他们的教育范围。在该项目中，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，而美国院校的学生将前往哥廷根大学。羧酸衍生物的氢化，如酯和酰胺，代表了一种生产合成有价值的醇和胺的原子经济的过程。最近在加氢合成胺和醇方面的进展依赖于二氢气体，然而，目前从化石燃料中产生的二氢气体对环境有害。在这个项目中，一个由耶鲁大学的尼莱·哈扎里和北卡罗来纳大学教堂山分校的亚历克斯·米勒组成的合作小组，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利用质子和电子还原酯类和酰胺类的电催化剂。该方法将利用对最近开发的酮还原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，并确定它们的热力学和动力学水合性。除了有希望的更可持续的合成方法外，电化学氢化很可能成为一种对官能团(如酸性中心)更具容忍性的氢化方法，并因此在学术界和工业中得到广泛应用。这项研究是在NSF-DFG领导机构电合成和电催化活动(NSF-DFG eChem)机会NSF 20-578下资助的。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。