Electrochemical nitration with nitrite

Aromatic nitration has tremendous importance in organic chemistry as nitroaromatic compounds serve as versatile building blocks. This study represents the electrochemical aromatic nitration with NBu4 NO2 , which serves a dual role as supporting electrolyte and as a safe, readily available, and easy-to-handle nitro source. Stoichiometric amounts of 1,1,1-3,3,3-hexafluoroisopropan-2-ol (HFIP) in MeCN significantly increase the yield by solvent control. The reaction mechanism is based on electrochemical oxidation of nitrite to NO2 , which initiates the nitration reaction in a divided electrolysis cell with inexpensive graphite electrodes. Overall, the reaction is demonstrated for 20 examples w…

Metallfreie, elektrochemische Synthese von Sulfonamiden direkt aus (Hetero)arenen, SO 2 und Aminen

Frontispiece: Metal‐Free Electrochemical Synthesis of Sulfonamides Directly from (Hetero)arenes, SO 2 , and Amines

Metal‐Free Electrochemical Synthesis of Sulfonamides Directly from (Hetero)arenes, SO2, and Amines

Abstract Sulfonamides are among the most important chemical motifs in pharmaceuticals and agrochemicals. However, there is no methodology to directly introduce the sulfonamide group to a non‐prefunctionalized aromatic compound. Herein, we present the first dehydrogenative electrochemical sulfonamide synthesis protocol by exploiting the inherent reactivity of (hetero)arenes in a highly convergent reaction with SO2 and amines via amidosulfinate intermediate. The amidosulfinate serves a dual role as reactant and supporting electrolyte. Direct anodic oxidation of the aromatic compound triggers the reaction, followed by nucleophilic attack of the amidosulfinate. Boron‐doped diamond (BDD) electro…

Frontispiz: Metallfreie, elektrochemische Synthese von Sulfonamiden direkt aus (Hetero)arenen, SO 2 und Aminen

CCDC 2032478: Experimental Crystal Structure Determination

Related Article: Stephan P. Blum, Tarik Karakaya, Dieter Schollmeyer, Artis Klapars, Siegfried R. Waldvogel|2021|Angew.Chem.,Int.Ed.|60|5056|doi:10.1002/anie.202016164