Urea‐ and Thiourea‐Catalyzed Aminolysis of Carbonates

Abstract The aminolysis of (poly)carbonates by (poly)amines provides access to non‐isocyanate polyurethanes (NIPUs) that are toxic‐reagent‐free analogues of polyurethanes (PUs). Owing to their low reactivity, the ring opening of cyclic carbonates requires the use of a catalyst. Herein, we report that the more available and cheaper ureas could advantageously be used for catalyzing the formation of NIPUs at the expense of the thiourea analogues. In addition, we demonstrate a medium‐range p K a of the (thio)urea and an unqeual substitution pattern is critical for controlling the efficiency of the carbonate opening.