Abstract An efficient method for isocyanate formation from N ‐Boc carbamates was developed utilizing a Hendrickson “POP” reagent as a dehydrating agent. By using this reagent, isocyanates were formed preferentially from N ‐Boc carbamates over other carbamates. The reaction could be paired with successive reactions such as Friedel–Crafts‐type cyclization and urea formation.