Copper-Catalyzed Cascade Substitution/Cyclization of N-Isocyanates: A Synthesis of 1-Aminobenzimidazolones

A copper-catalyzed cascade reaction of in situ generated nitrogen-substituted isocyanates (N-isocyanates) and 2-iodoanilines has been developed. The cascade relies on the base-catalyzed substitution of masked N-isocyanates, followed by Cu(I)-catalyzed coupling to afford a variety of 1-amino-benzimidazolones in moderate to excellent yields. This is the first example of a transition-metal-catalyzed cascade reaction involving N-isocyanate intermediates.