Substrate-controlled divergent remote C-H and N-H polyfluoroarylation of 2-aminopyrimidines with polyfluoroarenes via Pd(II)/Pd(0) catalysis.

Substrate-controlled product divergence in the reaction of 2-aminopyrimidines with polyfluoroarenes under palladium catalysis is demonstrated for the first time. The reaction of secondary N -alkylpyrimidine-2-amines with polyfluoroarenes leads to C5-H polyfluoroarylation via C-H/C-H coupling, while secondary N -aryl substituents yield N-H polyfluoroarylation, forming triarylamines.