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

Ru(III)-PhI(OAc), 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.

Cu(I)-Catalyzed C(sp)-H Functionalization of Amino Acids with Benzimidate and Reactive Oxygen Species (ROS) To Synthesize Triazines and 2-Pyrrolidinones.

An easily accessible Cu(I)-catalyzed regioselective oxidative C-N/C-O cross-coupling organic transformation has been disclosed for the syntheses of variably functionalized triazines and N-benzoylpyrrolidin-2-ones through the involvement of C(sp)-H bond functionalization, which is unknown in the literature. This general synthetic method is extended for decarboxylative oxidation of amino acids to install carbonyl functionality. It facilitates the formation of 2-3 new bonds through the cross-coupling strategy involving benzimidates, amino acids, and in situ-generated reactive oxygen species (ROS) from the aerial O as the sole oxidant.