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Adv."],"published-print":{"date-parts":[[2025,12,12]]},"abstract":"<jats:p>The research on the coordination chemistry and catalytic applications of sodium ions is of great importance. Inspired by the sodium ions\u2013activated enzymes, we explored a sodium complex based on the synergistic coordination of polyfluorophosphate anions and water molecules. X-ray crystallography and computational chemistry revealed its unique spatial structure and highlighted the activation state of the water molecules within the chiral cavity. Furthermore, we have successfully applied the sodium complex in the catalysis of \u03b1-ketoimine\u2013type 1,2-rearrangement, overcoming challenges of background reaction and competitive inhibition, ultimately achieving the construction of a series of chiral N-fused polycyclic isoquinolines with remarkable enantioselectivity. Mechanism studies shown that sodium complex activate and regulate water molecules to achieve highly stereoselective hydration process in the chiral environment and generate the key chiral 1,2-diol intermediate. Our research brings insights into the design and application of group 1 metal complexes and provides an approach to the development of asymmetric 1,2-rearrangement reactions.<\/jats:p>","DOI":"10.1126\/sciadv.ady4294","type":"journal-article","created":{"date-parts":[[2025,12,12]],"date-time":"2025-12-12T18:58:57Z","timestamp":1765565937000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":1,"title":["Chiral sodium complex\u2013catalyzed asymmetric cascade cycloaddition\/hydration\/1,2-rearrangement"],"prefix":"10.1126","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8879-1956","authenticated-orcid":true,"given":"Ming","family":"Zhang","sequence":"first","affiliation":[{"name":"Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China."},{"name":"School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen 518055, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-2009-541X","authenticated-orcid":true,"given":"Yuanlin","family":"Wei","sequence":"additional","affiliation":[{"name":"Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Man","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen 518055, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Shiyu","family":"Xu","sequence":"additional","affiliation":[{"name":"Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ying","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen 518055, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yuhong","family":"Yang","sequence":"additional","affiliation":[{"name":"School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen 518055, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7528-2036","authenticated-orcid":true,"given":"Guofeng","family":"Li","sequence":"additional","affiliation":[{"name":"School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen 518055, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4719-9921","authenticated-orcid":true,"given":"Rui","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Pharmacy, Shenzhen University Medical School, Shenzhen University, Shenzhen 518055, China."},{"name":"Institute of Materia Medica and Research Unit of Peptide Science, Chinese Academy of Medical Sciences, Peking Union Medical College, Beijing 100050, China."}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3489-0633","authenticated-orcid":true,"given":"Liang","family":"Hong","sequence":"additional","affiliation":[{"name":"Guangdong Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China."}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.R116.737833"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.R500023200"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1152\/physrev.00008.2006"},{"key":"e_1_3_2_5_2","doi-asserted-by":"crossref","unstructured":"M. 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