Convergent Paired Electrochemical Synthesis of Azoxy and Azo Compounds: An Insight into the Reaction Mechanism

Abstract

A convergent paired electrochemical method was developed for the synthesis of azoxy and azo compounds starting from the corresponding nitroarenes. We propose a unique mechanism for electrosynthesis of azoxy and azo compounds. We find that both anodic and cathodic reactions are responsible for the synthesis of these compounds. The synthesis of azoxy and azo derivatives have been successfully performed in an undivided cell, using carbon rod electrodes, by constant current electrolysis at room temperature.

Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

“…[334] Despite its high stability, Ni 3 Fe-MOF-OH can be used to synthesize azo-and azoxy-aromatic compounds (Figure 33e,f) with good yields and FE, making it an attractive synthetic tool. [332] Copyright 2021, American Chemical Society. c) An electrochemical synthesis of symmetric dispiro and spiropyrimidine derivatives based on the reduction of paranitrophenol.…”

“…Sadatnabi et al have developed a method based on paired electrochemical reactions for synthesizing nitroarenes into azoxy and azo compounds ( Figure 33 a ). [ 332 ] An undivided cell is successfully used to synthesize azoxy and azo derivatives via constant current electrolysis with carbon rod electrodes (Figure 33b ).…”

“…Reproduced with permission. [ 332 ] Copyright 2021, American Chemical Society. c) An electrochemical synthesis of symmetric dispiro and spiropyrimidine derivatives based on the reduction of paranitrophenol.…”

“…b) Possible reaction mechanism. Reproduced with permission [332]. Copyright 2021, American Chemical Society.…”

Photo-induced redox cascade reaction of nitroarenes and amines

“…[15][16][17][18][19] Electrochemical reduction provides a greener and milder route to azoxy-, azo-, hydrozo-and amino-derivatives from nitroarenes (Scheme 1b). [20][21][22][23][24] However, the wide product distribution is still a critical issue for this strategy due to the multiple electron transfer process.…”