Polymer‐Supported Organic Mediators for Organic Electrosynthesis: Established Architectures and Applications

Although organic electrosynthesis is regarded as an inherently green approach, its sustainability must be demonstrated beyond the mere use of electricity as a reagent, requiring the integration of broader principles, such as catalyst recovery and reuse. An underexplored approach is the use of polymer‐supported redox mediators or redox polymers, which can be either immobilized on the electrode surface or recovered and recycled. This review surveys the current literature on the application of organic redox polymers in organic electrosynthesis, covering redox polymer design, physicochemical characteristics, integration into electrochemical systems, and reaction methodology. Three established architectures of redox polymer application are compared: electrodes modified with ex situ synthesized or electropolymerized films, soluble redox polymers, and dispersed redox polymer systems. Existing literature examples demonstrate that redox polymer‐based methods can provide excellent yields and enantioselectivities, alter chemoselectivity, and enable transformations that are difficult to achieve with small‐molecule mediators. Nevertheless, the current scope of reactions, mediators, and polymer varieties remains narrow. Given the largely unrealized design space for these materials, redox polymers represent a significant opportunity for the development of sustainable electroorganic methodologies.