Construction of Polymers with Highly Dispersed Reactive Phases and Open Pores for Catalyzing the Efficient Synthesis of CO2 to α‐Methylene Cyclic Carbonates

Selective capture of carbon dioxide as a C1 feedstock for the preparation of high‐value chemicals has been recognised as an important way to mitigate the crisis. In this work, a new heterogeneous catalyst, Cu@CP‐PII, was developed through the rational construction of an open‐pore organic skeleton, which is easy to synthesise and highly efficient. With the synergistic effect between the high CO₂ affinity of the porous skeleton and the highly dispersed Cu(I) sites of the activated alkynes, it can be used for the efficient preparation of α‐methylene cyclic carbonates at ambient temperature and pressure. The structure and morphology were exhaustively characterised by Solid State ¹³C‐NMR, FT‐IR, XPS, TEM and N₂ adsorption‐desorption tests, and this catalyst possessed a high surface area of 273.7 m² ⋅ g⁻¹ and uniformly dispersion of CuI. To test its catalytic activity, Cu@CP‐PII in an amount of only 0.4 mol% was used as a catalyst for the carboxylative cyclization reaction of propargylic alcohols with CO₂, which resulted in substrate conversions up to 100 % and yields greater than 99 %. In addition, controlled experiments and mechanistic elucidation confirmed that anhydrous and low temperatures are necessary to achieve high selective control of the target product α‐methylene cyclic carbonates.