Organic Electrochemistry: Expanding the Scope of Paired Reactions

Abstract

Paired electrochemical reactions allow the optimization of both atom and energy economy of oxidation and reduction reactions. While many paired electrochemical reactions take advantage of perfectly matched reactions at the anode and cathode, this matching of substrates is not necessary. In constant current electrolysis, the potential at both electrodes adjusts to the substrates in solution. In principle, any oxidation reaction can be paired with any reduction reaction. Various oxidation reactions conducted on the anodic side of the electrolysis were paired with the generation and use of hydrogen gas at the cathode, showing the generality of the anodic process in a paired electrolysis and how the auxiliary reaction required for the oxidation could be used to generate a substrate for a non-electrolysis reaction. This is combined with variations on the cathodic side of the electrolysis to complete the picture and illustrate how oxidation and reduction reactions can be combined.

The interface is a tunable dimension in electricity‐driven organic synthesis

“…For detailed highlights of past and recent work on the scope of electroorganic synthetic methods advanced and discovered, we direct the reader to several reviews in the field. [4][5][6][7][18][19][20][21]23,[46][47][48] It is well-established how physical electrochemical tools that delineate current-voltage relationships can be utilized to uncover mechanistic insights into electroorganic processes; however, these reviews primarily focus on the homogeneous chemistry of electrochemical systems. 22,[49][50][51] We note that the electrode materials' impact on electrosynthetic processes has been extensively documented, 11 and this perspective is not intended to address practical concerns associated with choosing suitable electrode materials, for example, suppressing materials' corrosion or deposition of insulating organic layers, a topic that has been recently covered.…”

“…This perspective adds to the growing literature of electroorganic synthesis. For detailed highlights of past and recent work on the scope of electroorganic synthetic methods advanced and discovered, we direct the reader to several reviews in the field 4–7,18–21,23,46–48 . It is well‐established how physical electrochemical tools that delineate current–voltage relationships can be utilized to uncover mechanistic insights into electroorganic processes; however, these reviews primarily focus on the homogeneous chemistry of electrochemical systems 22,49–51 .…”

Controlling the Hydrophilicity of the Electrochemical Interface to Modulate the Oxygen-Atom Transfer in Electrocatalytic Epoxidation Reactions

“…The past decades have seen a growing interest in the development of electrosynthesis as a powerful synthetic tool. This is because, beyond its innate sustainability when powered by renewables, , electrosynthesis possesses many advantages such as high functional group tolerance, mild conditions, ability to selectively conduct oxidation and reduction reactions at controlled potentials, and scalability. − Numerous anodic and cathodic reactions have been developed, allowing the forging of useful chemical bonds, − the chemoselective functionalization of peptides and proteins, and even the total synthesis of natural products for which chemical synthesis has no practical solution . Among these reactions, electrochemical oxygenation reactions are of particular interest as they allow for the direct and chemoselective functionalization of C–H and CC bonds forming industrially and pharmaceutically relevant chemical functions such as enones, ketones, − aldehydes, ,, lactams, lactones, alcohols, ,,, and epoxides. ,,− The efficient and environmentally friendly preparation of an epoxide moiety is of prime importance as this structure is found in numerous natural products with potential biological activities, − is a versatile building block in organic chemistry, , and plays an important role in industry. , …”

Controlling the Hydrophilicity of the Electrochemical Interface to Modulate the Oxygen-Atom Transfer in Electrocatalytic Epoxidation Reactions

“…This is because, beyond its innate sustainability when powered by renewables, 1,2 electrosynthesis possesses many advantages such as high functional group tolerance, mild conditions, ability to selectively conduct oxidation and reduction reactions at controlled potentials and scalability. [2][3][4][5] Numerous anodic and cathodic reactions have been developed, allowing the forging of useful chemical bonds, [2][3][4][5][6][7][8][9][10][11] the chemoselective functionalization of peptides and proteins 12 and even the total synthesis of natural products for which chemical synthesis has no practical solution. 13 Among these reactions, electrochemical oxygenation reactions are of particular interest as they allow for the direct and chemoselective functionalization of C-H and C=C bonds forming industrially and pharmaceutically relevant chemical functions such as enones, 14 ketones, [15][16][17][18][19][20][21][22] aldehydes, 16,19,23 lactams, 24 lactones, 25 alcohols 15,21,22,26 and epoxides.…”