Electrochemical C-H Sulfonylation of ,-Dialkylanilines: Sequential Dehydrogenative Cross-Coupling and Sulfonylation.

An electrochemical method enables direct sulfonylation of ,-dialkylaniline derivatives through sequential dehydrogenative cross-coupling and C-H-activated sulfonylation. This method utilizes sulfonyl hydrazides, facilitating the one-pot synthesis of ,,','-tetramethyl-3-arylsulfonyl-[1,1'-biphenyl]-4,4'-diamine derivatives from ,-dimethylaniline. Furthermore, it efficiently introduces arylsulfonyl groups at the ortho position of various ,-dialkylanilines. Optimized conditions include a CHCN solvent system, a carbon anode, a nickel cathode, and an -BuNBF electrolyte. The method demonstrates a broad substrate scope, achieving high yields across various arylsulfonyl hydrazides and ,-dialkylanilines without requiring transition metal catalysts or external oxidants, thereby providing an efficient route to sulfonylated aniline derivatives.