Ru(III)-PhI(OAc)2─A Combination for Generation of Isocyanate Intermediate from Benzimidate through a Rearrangement: Synthesis of Unsymmetrical Urea, Carbamate, and Chiral Analogues

Ru(III)-PhI(OAc)2, an unprecedented combination, is a highly efficient reagent system for the in situ generation of a valuable isocyanate intermediate from benzimidate synthons through a rearrangement. It unlocks a powerful platform for forming diverse C–N bonds, enabling the one-pot synthesis of an expansive array of valuable unsymmetrical ureas, carbamates, and their chiral analogues toward complex molecular structures with high selectivity and excellent yields. This new strategy not only exemplifies efficiency but also serves as a versatile tool for the construction of valuable molecular architectures, enhancing the scope and impact of modern synthetic chemistry.