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However, their stereoselective construction remains a long\u2010standing challenge in synthetic chemistry. Here, we report a copper\u2010catalyzed desymmetrization strategy enabled by rationally engineered PIM ligands that affords broad and modular access to structurally diverse P(V)\u2010stereogenic compounds. By harnessing the tunable Lewis acidity and well\u2010defined chiral environment of the catalyst\u2014together with the distinct mechanistic features of chiral Lewis acid catalysis\u2014this strategy overcomes the substrate scope limitations that have constrained traditional approaches. The method demonstrates broad functional group tolerance and delivers high levels of stereocontrol across seven distinct substitution patterns, including the efficient construction of chiral P\u2550S motifs previously considered synthetically challenging. Importantly, the approach enables efficient late\u2010stage derivatization of nucleosides and their analogs, thereby providing a general entry point to stereodefined P(V)\u2010containing bioactive molecules. This work not only expands the utility of transition\u2010metal Lewis acid catalysis in phosphorus chemistry, but also establishes a versatile framework for applications in drug discovery and nucleic acid\u2010based therapeutics where precise stereochemical control is essential.<\/jats:p>","DOI":"10.1002\/anie.202509807","type":"journal-article","created":{"date-parts":[[2025,6,17]],"date-time":"2025-06-17T11:59:36Z","timestamp":1750161576000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Modular Access to P(V)\u2010Stereogenic Compounds via Cu\u2010Catalyzed Desymmetrization of (Thio)Phosphonic Dichlorides"],"prefix":"10.1002","volume":"64","author":[{"given":"Hong\u2010Qing","family":"Yao","sequence":"first","affiliation":[{"name":"Frontiers Science Center for Transformative Molecules State Key Laboratory of Synergistic Chem\u2010Bio Synthesis School of Chemistry and Chemical Engineering Zhangjiang Institute for Advanced Study Shanghai Jiao Tong University  Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yue\u2010Ming","family":"Cai","sequence":"additional","affiliation":[{"name":"Frontiers Science Center for Transformative Molecules State Key Laboratory of Synergistic Chem\u2010Bio Synthesis School of Chemistry and Chemical Engineering Zhangjiang Institute for Advanced Study Shanghai Jiao Tong University  Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tian","family":"Xie","sequence":"additional","affiliation":[{"name":"Frontiers Science Center for Transformative Molecules State Key Laboratory of Synergistic Chem\u2010Bio Synthesis School of Chemistry and Chemical Engineering Zhangjiang Institute for Advanced Study Shanghai Jiao Tong University  Shanghai 200240 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Jiao Tong University  Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0785-8427","authenticated-orcid":false,"given":"Ming","family":"Shang","sequence":"additional","affiliation":[{"name":"Frontiers Science Center for Transformative Molecules State Key Laboratory of Synergistic Chem\u2010Bio Synthesis School of Chemistry and Chemical Engineering Zhangjiang Institute for Advanced Study Shanghai Jiao Tong University  Shanghai 200240 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