Electrocatalytic Anaerobic Oxidation of Benzylic Amines Enabled by Ferrocene-Based Redox Mediators
Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide The generation and functionalization of carbon- or nitrogen-centered radicals are of great interest for their potential synthetic utility. Here, we report the anaerobic electrocatalytic oxidation of two primary benzylic amines, benzylamine and 2-picolylamine, in the presence of a catalytic quantity of an electron deficient ferrocene derivative as a single-electron redox mediator. The use of the appropriate redox mediator prevented fouling of the electrode surface and significantly decreased the potential at which the catalytic oxidation reaction occurred. Simulation of the electrochemical results revealed an E r C i ′ catalytic process between the redox mediator and both substrates and significant difference in the electron transfer rate between the two substrates and electrochemically oxidized mediator. Through anaerobic controlled-potential electrolysis, we demonstrated a method with a Faradaic efficiency of 90% forming the desired coupled imine product of benzylamine oxidation while avoiding an excess of problematic overoxidation, hydrolysis, and other side reactions. Based on the electrochemical data along with the product analyses using IR and 1 H and 13 C NMR spectroscopies, the proposed mechanistic steps for the redox mediated electrocatalytic process were laid out.
Source: Organometallics
Authors: Amy L. Waldbusser, Shabnam Hematian
Institution: University of North Carolina at Greensboro
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4401525850