Dual Roles of Supporting Electrolytes in Organic Electrosynthesis

Abstract

Synthetic electro‐organic chemistry is advancing to a well‐established methodology in academic research and industry. The simple process control minimizes reagent waste and avoids using toxic and environmentally unfriendly redox agents, providing a feasible and sustainable alternative to conventional techniques. However, a fundamental disadvantage, is the necessity of ion‐conductive components within the electrolyte. The recovery of these supporting electrolytes, as well as simple product isolation, pose challenges for work‐up strategies. This review presents the following electrochemical protocols featuring a simple material‐ and resource‐saving strategy: the dual role of supporting electrolytes as conductivity enabling components and reagents or meditators. This review is the first to conclude and categorize dual role strategies for the supporting electrolytes. It may inspire electrochemists to advance the development and optimization of electrochemical synthesis protocols towards more material‐ and resource‐efficient reaction control.

Efficient and Sustainable Electrosynthesis of N-Sulfonyl Iminophosphoranes by the Dehydrogenative P–N Coupling Reaction

“…Based on these results, a reaction mechanism is proposed in which the iodide-based supporting electrolyte fulfills a dual role, serving as an ionic conductor while simultaneously acting as a redox mediator (Scheme ). First, iodide is oxidized at the anode to form I 2 and I 3 – . Then, phosphine I reacts with I 2 equivalent to form intermediate II , analogously to Kirsanov reactions. ,, This hypothesis is supported by a control experiment in which I 2 (1.0 equiv) instead of electric current was employed as the oxidizing agent (see the Supporting Information).…”