Three-Component CO2 Conversion to Carbonyl Carboxylates Catalyzed by a Copper-Based Metal-Organic Framework under Mild Conditions.

The conversion of CO2 into valuable chemicals is crucial for the sustainable carbon utilization. The three-component reaction of CO2 with propargylic alcohols and monohydric alcohols to form carbonyl carboxylates is highly attractive but typically requires noble-metal catalysts under harsh conditions. Here, we report a novel Cu-MOF (1) with 1D channels (4.1 × 3.0 Å) exhibiting high stability across a wide pH range (1-13) and in various organic solvents. Under mild conditions, 1 efficiently catalyzes the CO2-involved the three-component reaction, achieving >99% yield of carbonyl carboxylates. 1 demonstrates broad substrate generality and can be reused for at least five cycles without significant loss of activity. Mechanistic studies indicate a synergistic catalytic effect between the Cu centers and the porous framework. To the best of our knowledge, this work presents the first example of a 2D MOF capable of catalyzing this CO2-involved three-component transformation under mild conditions, offering a new noble-metal-free catalytic system for CO2 conversion.