Copper‐Catalyzed Remote para‐C−H Functionalization of Anilines with Sodium and Lithium Sulfinates

A copper‐catalyzed, cross‐dehydrogenative coupling of anilines with sodium and lithium sulfinates was developed. By using a cooperative reaction system with Mn(OAc)3 as stoichiometric co‐oxidant a highly selective para‐functionalization of anilines was accomplished. Various functional groups were tolerated and the desired products were obtained in high yields. This method not only provides a novel approach for the synthesis of arylsulfones but might also offer new opportunities for the development of copper‐catalyzed para‐selective C−H functionalizations. Para not ortho: A cross‐dehydrogenative coupling of anilines with sulfinic acid salts is reported. The cooperative reaction system with Cu(OAc)2 as catalyst and Mn(OAc)3 as stoichiometric co‐oxidant overrides the usual ortho‐selectivity of copper‐catalyzed directing group‐assisted C−H‐functionalizations and allows remote para‐selective C−H‐sulfonylation of anilines.