Fluorinative Cyclization of <i>ortho</i> -Diisocyanoarenes: One-Pot Synthesis of <i>N</i> -CF ₃ and <i>N</i> -CF ₂ H Benzimidazoles

N -Fluoroalkyl azoles are vital drug motifs, yet their synthesis remains challenging. We report a one-pot synthesis of N -CF 3 and N -CF 2 H benzimidazoles from ortho -diisocyanoarenes using AgF or Py·9HF. The reaction involves fluorinating one isocyano group to an amino anion, followed by 5- endo-dig cyclization with an in situ nitrilium ion. This mild, efficient protocol offers good yields and scalability. Its utility is shown via diverse postfunctionalizations and the concise synthesis of an N -CF 3 omeprazole analogue.