Highly Efficient Multicomponent CO ₂ Conversion Facilitated by Synergistic Catalysis from N‐Heterocyclic Carbene and Copper in Metal–Organic Framework under Mild Conditions

ABSTRACT N‐heterocyclic carbenes (NHCs) demonstrate remarkable catalytic activity for CO 2 conversion, but their wide application is limited by air sensitivity and the requirement of strongly alkaline reaction conditions. Herein, an NHC‐CO 2 ‐functionalized metal‐organic framework (1‐NHC‐CO 2 ) was constructed, in which the CO 2 ‐masked NHC moieties remain stable under ambient conditions. Upon thermal treatment, CO 2 is released to regenerate the active NHC sites, thereby facilitating CO 2 conversion without strongly alkaline reaction conditions. Thus, 1‐NHC‐CO 2 efficiently catalyzes a multicomponent reaction involving CO 2 , enabling the simultaneous synthesis of pharmaceutically relevant oxazolidinones and α ‐hydroxyl ketones from aminoethanol and alkynol at 50°C, while other heterogeneous catalysts require at least 80°C. 1‐NHC‐CO 2 exhibits broad substrate scope, excellent recyclability over five cycles, and efficient gram‐scale performance, exhibiting the promising practical application. Experimental and DFT studies reveal that Cu 2+ and NHC within MOF activate the C≡C bond and CO 2 , respectively. The synergistic catalysis between Cu 2+ sites and NHC moieties as the key factor responsible for the high catalytic performance, representing the first example of metal/NHC synergistic catalysis for CO 2 conversion. This work offers a facile strategy to integrate molecular‐level regulation in heterogeneous catalysts, offering guidance for the development of sustainable catalysts in green chemistry.