Nickel‐Catalyzed C−H Chalcogenation of Anilines

The C−H thiolation of aniline derivatives was accomplished with a versatile nickel(II) catalyst under ligand‐free conditions. The robust nature of the nickel catalysis system was reflected by the C−H thiolation with a good functional group tolerance and an ample scope, employing anilines possessing removable directing groups. The widely applicable nickel catalyst also allowed for aniline C−H selenylations, while mechanistic studies provided strong support that the rate‐determining step is the C−H activation.