Electroorganic synthesis has become an established, useful, and environmentally benign alternative to classic organic synthesis for the oxidation or the reduction of organic compounds. In this context, the use of redox mediators to achieve indirect processes is attaining increased significance, since it offers many advantages compared to a direct electrolysis. Kinetic inhibitions that are associated with the electron transfer at the electrode/electrolyte interface, for example, can be eliminated and higher or totally different selectivity can be achieved. In many cases, a mediated electron transfer can occur against a potential gradient, meaning that lower potentials are needed, reducing the probability of undesired side-reactions. In addition, the use of electron transfer mediators can help to avoid electrode passivation resulting from polymer film formation on the electrode surface. Although the principle of indirect electrolysis was established many years ago, new, exciting and useful developments continue to be made. In recent years, several new types of redox mediators have been designed and examined, a process that can be accomplished more efficiently and purposefully using modern computational tools. New protocols including, the development of double mediatory systems in biphasic media, enantioselective mediation and heterogeneous electrocatalysis using immobilized mediators have been established. Furthermore, the understanding of mediated electron transfer reaction mechanisms has advanced. This review describes progress in the field of electroorganic synthesis and summarizes recent advances.

Redox catalysis in organic electrosynthesis: basic principles and recent developments.

Organic syntheses with electrochemically regenerable redox systems

The reactions of electrochemical splitting may be successfully used for removal of protecting groups. Theoretical and preparative aspects of the method of electro-deprotection are discussed, and examples of its use are given. The removal often requires high potentials. The use of modified protecting groups (“inner activation”) or of catalysts (electron carriers) which facilitate electron transfer against the standard potential gradient (“external activation”), can greatly increase the scope of the electrochemical method.

Electro‐Deprotection—Electrochemical Removal of Protecting Groups

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do electrochemistry and photoredox catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) that enable bond formations not constrained by the rules of ionic or 2 electron (e) mechanisms. Instead, they enable 1e mechanisms capable of bypassing electronic or steric limitations and protecting group requirements, thus enabling synthetic chemists to disconnect molecules in new and different ways. However, while providing access to similar intermediates, electrochemistry and photoredox catalysis differ in several physical chemistry principles. Understanding those differences can be key to designing new transformations and forging new bond disconnections. This review aims to highlight these differences and similarities between electrochemistry and photoredox catalysis by comparing their underlying physical chemistry principles and describing their impact on electrochemical and photochemical methods.

Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis.

Electrochemical reduction of graphene oxide films in aqueous and organic solutions

Cathodic cleavage of carbon-oxygen bonds (V). direct and indirect electrochemical reduction of epoxides

Coupure cathodique de liaisons carbone-oxygene—I reduction electrochimique d'alcools insatures application a la reduction tetraelectronique de certaines cetones en carbures

Coupure cathodique de liaisons carbone-oxygene—III Reduction de pinacols sur electrode de mercure—une possibilite de rupture electrochimique de liaisons carbone-carbone

Jacques Simonet

Papers

Cathodic cleavage of carbon-oxygen bonds (V). direct and indirect electrochemical reduction of epoxides

Coupure cathodique de liaisons carbone-oxygene—I reduction electrochimique d'alcools insatures application a la reduction tetraelectronique de certaines cetones en carbures

Coupure cathodique de liaisons carbone-oxygene—III Reduction de pinacols sur electrode de mercure—une possibilite de rupture electrochimique de liaisons carbone-carbone

Cathodic behaviour of p-toluenesulfonamides in organic solvents

Electrochemical cleavage of sulphones(II) — the influence of the electrogenerated bases in the cathodic reduction of allylic and benzylic sulphones