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We report the first copper\u2010catalyzed enantioselective hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2\u2010diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50\u2009% conversion, our approach employs a distinct dynamic kinetic asymmetric transformation mechanism, achieving complete conversion of racemic starting materials. This reaction is compatible with a broad range of aromatic and aliphatic terminal alkynes, producing products with high yields (up to 95\u2009%), exclusive\n                    <jats:italic>cis<\/jats:italic>\n                    selectivity, and exceptional regio\u2010 and enantioselectivity (&gt;20\u2009:\u20091\u2005r.r. and up to 96\u2009%\u2005ee). The resulting products were further transformed into a diverse array of enantioenriched P\u2010stereogenic scaffolds. Preliminary mechanistic studies were conducted to elucidate the reaction details.\n                  <\/jats:p>","DOI":"10.1002\/anie.202415314","type":"journal-article","created":{"date-parts":[[2024,10,5]],"date-time":"2024-10-05T12:39:32Z","timestamp":1728131972000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":33,"title":["Copper\u2010Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes"],"prefix":"10.1002","volume":"64","author":[{"given":"Jie","family":"Kang","sequence":"first","affiliation":[{"name":"State Key Laboratory of Medical Chemical Biology College of Pharmacy Nankai University  38 Tongyan Road, Jinnan District 300350 Tianjin P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kang","family":"Ding","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Medical Chemical Biology College of Pharmacy Nankai University  38 Tongyan Road, Jinnan District 300350 Tianjin P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Si\u2010Mu","family":"Ren","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Medical Chemical Biology College of Pharmacy Nankai University  38 Tongyan Road, Jinnan District 300350 Tianjin P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wen\u2010Jun","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Medical Chemical Biology College of Pharmacy Nankai University  38 Tongyan Road, Jinnan District 300350 Tianjin P.\u2005R. 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