Dibenzothiophene Sulfoximine as an NH3 Surrogate in the Synthesis of Primary Amines by Copper‐Catalyzed C−X and C−H Bond Amination

Readily accessible dibenzothiophene sulfoximine is an NH3 surrogate allowing the preparation of free anilines by copper‐catalyzed cross‐coupling reactions with aryl iodides or amides followed by radical S−N bond cleavage. The one‐pot/two‐step reactions sequence leads to the aminated products in good yields. A useful substitute: Dibenzothiophene sulfoximine is an NH3 surrogate allowing halo arenes and amides to be converted into aminated analogues by copper‐catalyzed Buchwald–Hartwig‐type or dehydrogenative C−H/N−H cross‐coupling reactions followed by radical sulfoxide cleavage.