C–C and C–N bond formation in electro-oxidation reactions of aromatic compounds

• Published in: Current research in green and sustainable chemistry 2024, Vol.8, p.100406, Article 100406
• Main Authors: Kononov, A., Strekalova, S., Kobeleva, E., Savelyev, G., Zlygostev, A., Khvorova, M., Morozov, V., Babaeva, O., Budnikova, Y.
• Format: Article
• Language: English
• Subjects: Anilide; Biaryl; C–C coupling; C–H functionalization; C–N bond formation; Dimer; Electro-oxidation; Metal-free
• ISSN: 2666-0865; 2666-0865
• DOI: 10.1016/j.crgsc.2024.100406

Atom-economical, eco-efficient, metal- and chemical oxidant-free formation of C–C and C–N bond from C(sp2)−H and C(sp3)−H of arenes toward the direct synthesis of biaryls and anilides or N-benzylamides under mild electro-oxidative conditions is described. The products of C–C and C–N coupling are obtained in up to 88% yields. Aromatic substrates that are oxidized at potentials less positive than +2 V or have bulky bromine or iodine substituents undergo homo-coupling reactions by anodic oxidation to form biaryls or dimers. Aromatic substrates that are difficult to oxidize (Eox > +2 V) preferentially form anilides and N-benzylamides upon anodic oxidation. The presence of a chlorine substituent on the aromatic ring leads to the formation of both biaryls and anilides during electro-oxidation. [Display omitted] •Electrooxidation of arenes to anilides or biaryls depend on the nature of substrate.•The oxidation potential is crucial for C–C or C–N bond formation selectivity.•Atom-economical, eco-efficient, one step electrosynthesis of dimers and anilides or N-benzylamides is proposed.