Chiral Phosphoric Acid–Functionalized Three‐Dimensional Covalent Organic Frameworks with Exceptional Chemical Stability for Asymmetric Catalysis

Abstract

Abstract The design of three‐dimensional covalent organic frameworks (3D COFs) incorporating chiral phosphoric acids represents a promising strategy to enhance enantioselectivity in asymmetric catalysis while providing good framework stability, but their development remains a significant challenge. Herein, by using the multivariate approach, we report the construction of two highly crystalline chiral phosphoric acid‐functionalized 3D COFs with the 4‐fold interpenetrated qtz topology. Notably, the resulting frameworks exhibit exceptional chemical stability, remaining crystallinity even in 12 M HCl, saturated NaOH, and boiling water. Moreover, benefiting from the confined chiral porous architecture, these COFs deliver good activity, enantioselectivity, and recyclability in asymmetric N, N ‐acetalization reactions, significantly outperforming their homogeneous analogues. This work not only reports a highly stable chiral phosphoric acid‐functionalized 3D COF for asymmetric catalysis, but also provides a foundation for constructing robust, reusable heterogeneous chiral organocatalysts.