A heterogeneous ZIF-90-based catalyst functionalized with COOH and with a porous structure was facilely prepared for efficient CO adsorption and activation to undergo reductive -formylation with a wide range of amines (15 examples) to furnish -formamides (78-94% yields). The -COO species generated by an interaction with amine acts as a key species for activating hydrosilane to capture CO, and remarkably facilitates a cascade C-N coupling and hydrogenation process. Our findings show a facile strategy for the rational construction of robust active sites for reductive CO valorization.
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