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

The critical aspects of the corrosion of metal electrodes in cathodic reductions are covered. We discuss the involved mechanisms including alloying with alkali metals, cathodic etching in aqueous and aprotic media, and formation of metal hydrides and organometallics. Successful approaches that have been implemented to suppress cathodic corrosion are reviewed. We present several examples from electroorganic synthesis where the clever use of alloys instead of soft neat heavy metals and the application of protective cationic additives have allowed to successfully exploit these materials as cathodes. Because of the high overpotential for the hydrogen evolution reaction, such cathodes can contri…

Recent advances in the electrochemical reduction of substrates involving N−O Bonds

Intermolecular oxidative dehydrogenative 3,3′-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+: total synthesis of shandougenine B

With an excess of a strong acid, 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ) is shown to promote metal-free intermolecular oxidative dehydrogenative (ODH) 3,3'-coupling of 2-aryl-benzo[b]furans and 2-aryl-benzo[b]thiophenes up to 92% yield as demonstrated with 9 substrates. Based on the analysis of oxidation potentials and molecular orbitals combined with EPR, NMR and UV-Vis observations, the studied reaction is initiated by a DDQ-substrate charge transfer complex and presumably proceeds via oxidation of the substrate into an electrophilic radical cation that further reacts with another molecule of a neutral substrate. The coupling reactivity can easily be predicted from the oxidation potent…

Front Cover: Selective and Scalable Electrosynthesis of 2H ‐2‐(Aryl)‐benzo[ d ]‐1,2,3‐triazoles and Their N‐Oxides by Using Leaded Bronze Cathodes (Chem. Eur. J. 25/2020)

Carbocatalytic Oxidative Dehydrogenative Couplings of (Hetero)Aryls by Oxidized Multi‐Walled Carbon Nanotubes in Liquid Phase

HNO3-oxidized carbon nanotubes catalyze oxidative dehydrogenative (ODH) carbon-carbon bond formation between electron-rich (hetero)aryls with O-2 as a terminal oxidant. The recyclable carbocatalytic method provides a convenient and an operationally easy synthetic protocol for accessing various benzofused homodimers, biaryls, triphenylenes, and related benzofused heteroaryls that are highly useful frameworks for material chemistry applications. Carbonyls/quinones are the catalytically active site of the carbocatalyst as indicated by model compounds and titration experiments. Further investigations of the reaction mechanism with a combination of experimental and DFT methods support the compet…

Selective and Scalable Electrosynthesis of 2H-2-(Aryl)-benzo[d]-1,2,3-triazoles and Their N-Oxides by Using Leaded Bronze Cathodes.

Abstract Electrosynthesis of 2H‐2‐(aryl)benzo[d]‐1,2,3‐triazoles and their N‐oxides from 2‐nitroazobenzene derivatives is reported. The electrolysis is conducted in a very simple undivided cell under constant current conditions with a leaded bronze cathode and a glassy carbon anode. The product distribution between 2H‐2‐(aryl)benzo[d]‐1,2,3‐triazoles and their N‐oxides can be guided by simply controlling the current density and the amount of the charge applied. The reaction tolerates several sensitive functional groups in reductive electrochemistry. The usefulness and the applicability of the synthetic method is demonstrated by a formal synthesis of an antiviral compound.