Ru(III)-PhI(OAc)<sub>2</sub>A Combination\nfor Generation of Isocyanate Intermediate from Benzimidate through\na Rearrangement: Synthesis of Unsymmetrical Urea, Carbamate, and Chiral\nAnalogues

Ru(III)-PhI(OAc)<sub>2</sub>, an unprecedented combination,\nis\na highly efficient reagent system for the in situ generation of a\nvaluable isocyanate intermediate from benzimidate synthons through\na rearrangement. It unlocks a powerful platform for forming diverse\nC–N bonds, enabling the one-pot synthesis of an expansive array\nof valuable unsymmetrical ureas, carbamates, and their chiral analogues\ntoward complex molecular structures with high selectivity and excellent\nyields. This new strategy not only exemplifies efficiency but also\nserves as a versatile tool for the construction of valuable molecular\narchitectures, enhancing the scope and impact of modern synthetic\nchemistry.