Cu(I)‐Anchored Amine‐Rich Covalent‐Organic Polymer for Sustainable Utilization of CO₂ in the Synthesis of Valuable Chemicals and C─C Bond Formation Reactions.

Selective chemical fixation of carbon dioxide (CO₂) offers a promising approach to mitigate rising atmospheric CO₂ levels while facilitating the synthesis of valuable commodity chemicals, thereby supporting the circular economy. The cycloaddition of CO₂ to form α‐alkylidene cyclic carbonates is particularly attractive due to its utilization of CO₂, a low‐cost C1 feedstock, in a reaction with 100% atom economy. In this study, we have developed an amine‐functionalized, nitrogen‐rich covalent organic polymer (COP), SNW‐1@NH₂, which strongly supports the grafting of Cu(I) ions within its porous framework. The synergistic interaction between SNW‐1@NH₂ and Cu(I) enhances the catalytic activity for the CO₂ cycloaddition with propargylic alcohol, resulting in the formation of α‐alkylidene cyclic carbonates at room temperature without the need for precious metal catalysts. Notably, the catalyst exhibits a broad substrate scope with high recyclability and maintains its structural integrity and catalytic performance. Additionally, the SNW‐1@NH₂ was successfully applied in the catalytic Knoevenagel condensation of benzaldehyde with cyanoacetamide, demonstrating a broad substrate scope, excellent recyclability, and stability. Mechanistic studies were performed to elucidate the reaction pathways for both catalytic processes. This work underscores the potential of nitrogen‐rich porous materials in addressing the critical environmental challenges and expanding catalytic applications. [ABSTRACT FROM AUTHOR]