Organic ligand and solvent free oxidative carbonylation of amine over Pd/TiO2 with unprecedented activity

Abstract

A highly active Pd/TiO₂ catalyst system was prepared and applied in the oxidative carbonylation of amines to ureas with ultra-low Pd content under organic ligand and solvent free conditions. The catalytic turnover frequencies (TOFs, moles of amines converted per mole of Pd per h) were 126 000 and 250 000 h⁻¹ for the production of diphenylurea and dibenzylurea, respectively. An expanded substrate scope including the electron-rich and electron-deficient anilines, primary aliphatic amines, secondary amines was also established. This work offers a straightforward, step economic, and green methodology for the efficient synthesis of valuable ureas.