Highly Stable Zr(IV)-Based Metal–Organic Frameworks with Chiral Phosphoric Acids for Catalytic Asymmetric Tandem Reactions

Heterogeneous Brønsted acid catalysts featuring high porosity, crystallinity, and stability have been of great interest for both fundamental studies and practical applications, but synthetically, they still face a formidable challenge. Here, we illustrated a ligand design strategy for directly installing chiral phosphoric acid catalysts into highly stable Zr-MOFs by sterically protecting them from coordinating with metal ions. A pair of chiral porous Zr(IV)-MOFs with the framework formula [Zr6O4(OH)8(H2O)4(L)2] were prepared from enantiopure 4,4',6,6'-tetra(benzoate) and -tetra(2-naphthoate) ligands of 1,1'-spirobiindane-7,7'-phosphoric acid. They share the same topological structure but differ in channel sizes, and both of them demonstrate excellent tolerance toward water, acid and base. Significantly enhanced Brønsted acidity was observed for the phosphoric acids that are uniformly distributed within the frameworks in comparison with the nonimmobilized acids. This not only facilitates the catalysis of asymmetric two-component tandem acetalization, Friedel-Crafts, and iso-Pictet-Spengler reactions but also promotes the catalysis of asymmetric three-component tandem deacetalization-acetalization and Friedel-Crafts reactions benefiting from the synergy with exposed Lewis acidic Zr(IV) sites. The enantioselectivities are comparable or favorable compared to those obtained from the corresponding homogeneous systems. The features of high reactivity, selectivity, stability, and recyclability for Zr(IV)-MOFs make them hold promise as a new type of heterogeneous acid catalyst for the eco-friendly synthesis of fine chemicals.