CAS: Electrochemical Ionic Hydrogenation: Promoting Carbonyl and Imine Reduction through Electrocatalysis

在化学系化学催化项目的支持下，罗格斯大学的Kate M. Waldie，新泽西州立大学正在研究利用电化学制备有价值的化学产品的策略。该项目的目标是开发使用可再生、可持续能源生产化学品的更可持续的方法。拟进行的研究将包括实验，以了解催化剂结构和反应条件如何结合以实现高反应效率和选择性。这些知识将在可持续化学制造的电催化剂设计中有重要的应用。该项目还将为学生提供合成化学、催化和电化学方面的培训。Waldie小组将继续开展外展活动，促进传统上代表性不足的群体的学生的公平和包容，包括一个名为“化学多样性”的系列研讨会，强调来自不同背景的化学家的职业和观点。Waldie博士还将为电化学教育开发新的讲座和实验教学资源。该项目将在Brønsted或Lewis酸促进剂的存在下，利用过渡金属氢化物配合物开发羰基和亚胺底物的电化学离子加氢。这种电催化加氢的方法避免了对氢气或化学计量还原剂的需要。然而，避免竞争性析氢反应（HER）是电化学还原反应面临的重大挑战。拟议的研究将利用详细的电化学、动力学和机理研究来检查底物与酸的活化如何指导金属氢化物配合物的反应活性，使其在HER上进行电化学加氢。本项目旨在建立一个热力学框架，优化金属氢化物电催化剂和酸促进剂的性能，以实现高选择性和高法拉第效率的底物还原。目的是研究一个大的反应范围，建立原理和方法来推进羰基和亚胺氢化的电气化，以实现可持续的有机合成。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 the support of the Chemical Catalysis program in the Division of Chemistry, Kate M. Waldie of Rutgers, The State University of New Jersey is studying strategies to prepare valuable chemical products using electrochemistry. The goal of this project is to develop more sustainable methods for producing chemicals using renewable, sustainable energy. The proposed research will involve experiments to understand how catalyst structure and reaction conditions combine to achieve high reaction efficiency and selectivity. This knowledge will have important applications in electrocatalyst design for sustainable chemical manufacturing. The project will also provide training for students in synthetic chemistry, catalysis, and electrochemistry. The Waldie group will continue to engage in outreach activities that promote the equity and inclusion of students from traditionally underrepresented populations, including a recurring symposium series entitled Diversity in Chemistry that highlights the careers and perspectives of chemists from diverse backgrounds. Dr. Waldie will also develop new lecture and laboratory teaching resources for electrochemistry education. This project will develop the electrochemical ionic hydrogenation of carbonyl and imine substrates using transition metal-hydride complexes in the presence of Brønsted or Lewis acid promotors. This electrocatalytic approach to hydrogenation circumvents the need for hydrogen gas or stoichiometric reductants. However, avoiding the competitive hydrogen evolution reaction (HER) is a significant challenge for electrochemical reduction reactions. The proposed research will utilize detailed electrochemical, kinetic, and mechanistic studies to examine how substrate activation with an acid can direct the reactivity of metal-hydride complexes toward electrochemical hydrogenation over HER. This project aims to establish a thermodynamic framework in which the properties of the metal-hydride electrocatalyst and acid promoter are optimized to achieve high selectivity and high faradaic efficiency for substrate reduction. The goal is to investigate a large reactivity scope and establish principles and methods to advance the electrification of carbonyl and imine hydrogenation for sustainable organic synthesis.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.