Iterative C−H Functionalization Leading to Multiple Amidations of Anilides

Polyaminobenzenes were synthesized by the ruthenium‐catalyzed iterative C−H amidation of anilides using dioxazolones as an amino source. This strategy could be implemented by the sequential activation of C−H bonds of formerly generated compounds by cascade chelation assistance of newly installed amide groups. Computational studies provided a rationale. Repeat performance: A ruthenium‐catalyzed cascade amidation of multiple C−H bonds of anilide has been developed. By using dioxazolone as amidating reagents, newly installed amide groups serve as an additional directing groups to drive subsequent C−H activation. This reaction provides a simple and mild approach to the preparation of polyaminobenzenes.