Alkylselenite-catalyzed Oxidative Carbonylation of Amines: Density Functional Theory Study

Abstract

Ureas and carbamates have been conventionally produced by the reaction of amines with phosgene. However, phosgenation processes raise severe environmental concerns, which are attributed to the toxicity of phosgene and the formation of corrosive hydrogen chloride as a co-product. The considerable industrial interest in replacing current phosgene-based processes prompted several methods using non-phosgene routes including carbonylation of amines or nitro compounds and carbomethoxylation of amines with dialkylcarbonates. Among these, catalytic oxidative carbonylation of an amine in the presence of alcohol has been studied most extensively. Catalytic systems based on precious metals such as Rh and Pd are commonly used for this purpose, but most of these catalytic systems suffer from either low reactivity or severe reaction conditions such as high temperature and pressures. Alkali metal selenites and imidazolium alkylselenites have also been successfully employed by our group for the oxidative carbonylation of aromatic amines to produce diarylurea and/or arylcarbamates (Eq. 1).