Electrochemistry, 3. Organic Electrochemistry

Abstract

The article contains sections titled: 1. Introduction 2. Perspectives of Electroorganic Reactions in Industry 3. Syntheses 3.1. Direct vs. Indirect or Mediated Electrochemical Reactions 3.2. Technically Important Processes Ordered by Reaction Classes 3.2.1. Electrochemical Substitution 3.2.2. Electrochemical Addition 3.2.3. Electrochemical Transformations of Functional Groups 3.2.4. Electrochemical Cleavage and Elimination 3.2.5. Electrochemical Coupling 3.2.6. Bioelectrosynthesis 3.3. Organic Electrochemistry for a Cleaner Environment 4. Experimental Factors and Techniques 4.1. Solvent ‐ Electrolyte Systems 4.2. Electrodes 4.2.1. Cathodes 4.2.2. Anodes 4.2.3. Other Factors Influenced by the Electrode Material 4.3. Electrochemical Cells 4.3.1. General Considerations 4.3.2. Cell Design 5. Economic Aspects

Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

“…15 − 19 Substrates can also be reduced electrochemically using inexpensive electrons ($0.006 mol –1 ) supplied directly by the cathode or indirectly using a mediator. 20 − 25 …”

“…In particular, platinum is commonly used as counter electrode in anodic oxidation reactions, and therefore its deterioration can have important consequences for the overall electrolysis. 25 , 32 Finally, we suggest some simple guidelines for the organic electrosynthesis community to remain aware of cathodic corrosion and take it into account. As a final note, we do not review corrosion through anodic oxide formation that is followed by cathodic reduction of the metal oxides, 44 − 46 cathodic corrosion of nanoparticles, 47 or open-circuit corrosion.…”

“…Reductions are fundamental in chemistry. Traditionally, substrates are reduced with dissolving metals (i.e., Na, K, Na/K, Li, Zn, Fe, Al, Ni), metal hydrides, or with hydrogen or hydrogen donors in the presence of a transition metal (TM) catalyst or a frustrated Lewis pair (FLP). − Substrates can also be reduced electrochemically using inexpensive electrons ($0.006 mol –1 ) supplied directly by the cathode or indirectly using a mediator. − …”

Organic Electrosynthesis: From Laboratorial Practice to Industrial Applications

“…Organic electrosynthesis, enabling the replacement of dangerous and toxic chemicals by electric current, or “clean” electrons, together with its high versatility, has attracted great attention at the laboratorial ,, and industrial scales in areas of fine chemicals, environmental mitigation, pharmaceuticals, agrochemicals, and others. , …”

Electrosynthesis Using a Recyclable Mediator–Electrolyte System Based on Ionically Tagged Phenyl Iodide and 1,1,1,3,3,3-Hexafluoroisopropanol

“…Such mediators are often employed to facilitate electron transfer between electrode and substrate and to influence the selectivity of the electrosynthetic process . Since both the supporting electrolyte and the mediator represents a source of waste and a key-expense factor, their recovery and reuse for multiple cycles is highly desirable for industrial applications. , …”