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Synthesis of a Pyridine–Zinc-Based Porous Organic Polymer for the Co-catalyst-Free Cycloaddition of Epoxides

He Li,Chunzhi Li,Jian Chen,Lina Liu,Qihua Yang

Graphical Pore it on : A bifunctionalized pyridine–zinc-based porous organic polymer, Py-Zn@MA, is synthesized and used for the co-catalyst-free cycloaddition of epoxides with CO 2 . The high activity of Py-Zn@MA is attributed to its bifunctional nature with ZnBr 2 and pyridine activating the epoxide in a cooperative way. The catalyst can be easily prepared on a large scale and shows good substrate universality for the cycloaddition of epoxides. The synthesis of solid catalysts for the co-catalyst-free cycloaddition of CO 2 has attracted much attention. Herein, we report a hierarchical porous organic polymer, Py-Zn@MA, that is able to catalyze the cycloaddition reaction of epoxides and CO 2 without using any additives or co-catalyst to afford turnover frequency (TOF) values as high as 250 and 97 h −1 at 130 °C by using pure and diluted CO 2 (simulating flue gas), respectively. These results are superior to those obtained from previously reported heterogeneous co-catalyst-free systems. The high activity of Py-Zn@MA is mainly attributed to its bifunctional nature with ZnBr 2 and pyridine activating the epoxide in a cooperative way. Notably, Py-Zn@MA can be easily prepared on a large scale without using any catalyst and the chemicals are cost effective. Moreover, Py-Zn@MA shows good substrate universality for the cycloaddition reactions of epoxides. Our designed porous organic polymer Py-Zn@MA material has the potential to serve as an efficient catalyst for the direct conversion of flue gas with epoxides into value-added cyclic carbonates.