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

University Of North Carolina At Chapel Hill, Chapel Hill NC

Investigators

Abstract

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.