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Herein, we report a copper\u2010photoredox catalytic system that enables the stereoselective generation of copper\u2010bound P\u2010centered radicals and their subequent stereoretentive transformations within a well\u2010defined chiral environment. The synergistic approach achieves unprecedented kinetic resolutions of racemic H\u2010phosphinates with \u03b1\u2010trifluoromethyl styrenes or\n                    <jats:italic>gem<\/jats:italic>\n                    \u2010difluorostyrenes, delivering 85 fluorine\u2010containing P\u2010chiral phosphinates with up to 98%\u00a0ee. The method thereby bridges a synthetic gap for these previously inaccessible, pharmacologically significant compounds. Mechanistic and computational studies reveal a stereochemical relay: enantiodiscriminatory binding of racemic substrates, photoinduced ligand\u2010to\u2010metal charge transfer (LMCT) for radical generation, and stereoretentive bond formation. By reconciling radical reactivity with stereochemical fidelity, our strategy establishes metallaphotoredox catalysis as a versatile paradigm for heteroatom\u2010centered stereochemistry.\n                  <\/jats:p>","DOI":"10.1002\/anie.202521100","type":"journal-article","created":{"date-parts":[[2025,11,18]],"date-time":"2025-11-18T07:19:30Z","timestamp":1763450370000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Copper\u2010Catalyzed Phosphorus Radical Transformations for the Assembly of P\u2010Stereogenic Architectures"],"prefix":"10.1002","volume":"65","author":[{"given":"Yujin","family":"Zi","sequence":"first","affiliation":[{"name":"College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Boxuan","family":"Yang","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ziqi","family":"Ye","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu\u2010Mei","family":"Lin","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qianyi","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Henan Normal University  Xinxiang China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Binju","family":"Wang","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4478-6880","authenticated-orcid":false,"given":"Lei","family":"Gong","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Xiamen University  Xiamen 361005 China"},{"name":"Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)  Xiamen China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,11,17]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/b111414j"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/b500511f"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar500365v"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201505090"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b08856"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.8b00209"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201903726"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.4c00638"},{"key":"e_1_2_7_9_1","first-page":"28034","volume":"146","author":"Garwood J. 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