Umpolung C–N Bond Formation Enabled by Rhodium-Catalyzed Arylation of Sulfilimines with Arylboronic Acids

A new type of umpolung C-N bond-forming approach enabled by Rh-catalyzed arylation of sulfilimines with arylboronic acids is reported, providing a versatile platform for the construction of various nitrogen-containing molecules. The key process is proposed to undergo 1,1-elimination at the sulfur atom triggered by the regioselective addition of an aryl-rhodium species to the S═N moiety creating a C-N bond to furnish an aminorhodium intermediate that is subsequently trapped by various electrophiles to give arylamines. This approach has also been extended to the three-component amination to furnish a diarylamine product via the creation of C-N-C bonds. This approach exhibits a broad substrate scope and wide functional-group compatibility under mild conditions, enabling the late-stage functionalization of complex molecules to prepare nitrogen-containing variants of drug candidates with potential therapeutic activity.