Ligandless Copper‐Catalyzed Coupling of Heteroaryl Bromides with Gaseous Ammonia

A range of different N‐ and S‐containing heterocyclic bromides can be efficiently coupled with gaseous ammonia in the presence of copper(II) acetylacetonate [Cu(acac) 2 ] as catalyst and in the absence of additional ligands. Unstable aminothiophenes and aminobenzothiophenes can be further reacted in situ to afford functionalized derivatives.