Electrochemical organic reactions: A tutorial review

Abstract

Although the core of electrochemistry involves simple oxidation and reduction reactions, it can be complicated in real electrochemical organic reactions. The principles used in electrochemical reactions have been derived using physical organic chemistry, which drives other organic/inorganic reactions. This review mainly comprises two themes: the first discusses the factors that help optimize an electrochemical reaction, including electrodes, supporting electrolytes, and electrochemical cell design, and the second outlines studies conducted in the field over a period of 10 years. Electrochemical reactions can be used as a versatile tool for synthetically important reactions by modifying the constant electrolysis current.

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

“…This concept of Functional Group Transfer Reagents (FGTRs) [14] has enabled access to unprecedentedly mild conditions for the release of radical species, and thus expended the chemical space through their broader utilization in synthetic organic chemistry. Selective and regulated production of the desired radical by activation of an appropriate FGTR can be carried out by photoredox catalysis, [15–22] irradiation of Electron Donor‐Acceptor (EDA) complexes, [23,24] electrochemistry, [25–29] electro‐photocatalysis, [30,31] the use of semiconductor materials, [32–34] metal catalysis [35–38] and other activation modes (Figure 1B).…”

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

“…[11][12][13] This concept of Functional Group Transfer Reagents (FGTRs) [14] has enabled access to unprecedentedly mild conditions for the release of radical species, and thus expended the chemical space through their broader utilization in synthetic organic chemistry. Selective and regulated production of the desired radical by activation of an appropriate FGTR can be carried out by photoredox catalysis, [15][16][17][18][19][20][21][22] irradiation of Electron Donor-Acceptor (EDA) complexes, [23,24] electrochemistry, [25][26][27][28][29] electro-photocatalysis, [30,31] the use of semiconductor materials, [32][33][34] metal catalysis [35][36][37][38] and other activation modes (Figure 1B).…”

Metal‐Free Electrochemical Reduction of Disulfides in an Undivided Cell under Mass Transfer Control

“…This strategy can be achieved by adjusting the electrode surface area available for the reaction and creating a significant imbalance between the working and the counter electrodes. [6,10,11] Under galvanostatic conditions, the electrode featuring a small surface area generates a very large current density and thus the electrolysis at that electrode becomes mass transport limited. This approach has scarcely been used in organic electrosynthesis for the generation of reactive intermediates from solvent molecules.…”

“…In addition to physical barriers, such as those incorporated in divided cells (Figure 1a), organic compounds can be prevented from reaching an electrode by implementing a mass transfer barrier. This strategy can be achieved by adjusting the electrode surface area available for the reaction and creating a significant imbalance between the working and the counter electrodes [6,10,11] . Under galvanostatic conditions, the electrode featuring a small surface area generates a very large current density and thus the electrolysis at that electrode becomes mass transport limited.…”