Cooperative Catalysis of Cyclic Carbonate Ring Opening: Application Towards Non-Isocyanate Polyurethane Materials

• Published in: European journal of organic chemistry 2015-05, Vol.2015 (13), p.2791-2795
• Main Authors: Lombardo, Vince M., Dhulst, Elizabeth A., Leitsch, Emily K., Wilmot, Nathan, Heath, William H., Gies, Anthony P., Miller, Matthew D., Torkelson, John M., Scheidt, Karl A.
• Format: Article
• Language: English
• Subjects: Amines; Catalysis; Cooperative catalysis; Cyclic carbonates; Polymers; Poly­urethane
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201500313

The reaction between cyclic carbonates and amines to produce hydroxyurethanes is an important alternative to current urethane chemistry. In order to address the issue of slow reaction rates, an efficient ring opening of cyclic carbonates with amines has been achieved utilizing cooperative catalysis. A new Lewis acid/Lewis base combination substantially decreases the reaction times for small molecule systems to reach complete conversion. Although triazabicyclodecene (TBD) has a substantial impact on the reaction rate, the addition of lithium triflate (LiOTf) as a co‐catalyst allows for the fastest ring opening reported in the current literature. Cooperative catalysis is also applied to the synthesis of polymers containing hydroxyurethane linkages and is able to achieve rapid conversion of the bis‐cyclic carbonate and diamine precursors when compared with the uncatalyzed reaction. Efficient ring opening of cyclic carbonates with amines is achieved by cooperative catalysis. A new Lewis acid/Lewis base combination accelerates this challenging and potentially industrially useful process. Its application towards the syntheses of non‐isocyanate polyurethanes (NIPUs) achieves rapid conversion of bis‐cyclic carbonate and diamine precursors vs. the uncatalyzed reaction.