Palladium-catalyzed monoamination of dihalogenated benzenes

The palladium-catalyzed monoamination of symmetric dibromobenzenes can be performed using a catalyst based on Pd2dba3 and BINAP in the presence of NaO(t-Bu). The analogous transformation of non-symmetric bromoiodobenzenes is most effectively performed with Xantphos as the ligand, while reactions with BINAP were non-selective. These transformations can be scaled uneventfully to >10 g quantities. They do not require drybox or Schlenk techniques, and all reagents are weighed out in air. The resulting monobromoanilines are versatile intermediates for further synthetic transformations.