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Herein, by using the multivariate approach, we report the construction of two highly crystalline chiral phosphoric acid\u2010functionalized 3D COFs with the 4\u2010fold interpenetrated\n                    <jats:bold>qtz<\/jats:bold>\n                    topology. Notably, the resulting frameworks exhibit exceptional chemical stability, remaining crystallinity even in 12\u00a0M 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                    <jats:italic>N, N<\/jats:italic>\n                    \u2010acetalization reactions, significantly outperforming their homogeneous analogues. This work not only reports a highly stable chiral phosphoric acid\u2010functionalized 3D COF for asymmetric catalysis, but also provides a foundation for constructing robust, reusable heterogeneous chiral organocatalysts.\n                  <\/jats:p>","DOI":"10.1002\/anie.202522928","type":"journal-article","created":{"date-parts":[[2026,1,16]],"date-time":"2026-01-16T13:23:16Z","timestamp":1768569796000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Chiral Phosphoric Acid\u2013Functionalized Three\u2010Dimensional Covalent Organic Frameworks with Exceptional Chemical Stability for Asymmetric Catalysis"],"prefix":"10.1002","volume":"65","author":[{"given":"Mengsi","family":"Li","sequence":"first","affiliation":[{"name":"College of Chemistry and Molecular Sciences Wuhan University  Wuhan 430072 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