{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T00:25:37Z","timestamp":1788308737144,"version":"build-2803163510"},"reference-count":89,"publisher":"Wiley","issue":"47","license":[{"start":{"date-parts":[[2023,10,19]],"date-time":"2023-10-19T00:00:00Z","timestamp":1697673600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21831005"],"award-info":[{"award-number":["21831005"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21991112"],"award-info":[{"award-number":["21991112"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22171183"],"award-info":[{"award-number":["22171183"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2023,11,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Fluorinated amino acids and related peptides\/proteins have been found widespread applications in pharmaceutical and agricultural compounds. However, strategies for introducing a C\u2212F bond into amino acids in an enantioselective manner are still limited and no such asymmetric catalysis strategy has been reported. Herein, we have successfully developed a Pd\/Cu\/Li ternary system for stereodivergent synthesis of chiral fluorinated amino acids. This method involves a sequential desymmetrization of geminal difluoromethylenes and allylic substitution with amino acid Schiff bases via Pd\/Li and Pd\/Cu dual activation, respectively. A series of non\u2010natural amino acids bearing a chiral allylic\/benzylic fluorine motif are easily synthesized in high yields with excellent regio\u2010, diastereo\u2010, and enantioselectivities (up to &gt;20\u2009:\u20091 dr and &gt;99\u2009% ee). A density functional theory (DFT) study revealed the F\u2212Cu interaction of the allylic substrate and the Cu catalyst significantly influence the stereoselectivity.<\/jats:p>","DOI":"10.1002\/anie.202313838","type":"journal-article","created":{"date-parts":[[2023,10,10]],"date-time":"2023-10-10T11:47:59Z","timestamp":1696938479000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":41,"title":["Desymmetrization of Geminal Difluoromethylenes using a Palladium\/Copper\/Lithium Ternary System for the Stereodivergent Synthesis of Fluorinated Amino Acids"],"prefix":"10.1002","volume":"62","author":[{"given":"Yicong","family":"Luo","sequence":"first","affiliation":[{"name":"Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Frontiers Science Center for Transformative Molecules School of Chemistry and Chemical Engineering Shanghai Jiao Tong University  800 Dongchuan Road Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuqi","family":"Ma","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Frontiers Science Center for Transformative Molecules School of Chemistry and Chemical Engineering Shanghai Jiao Tong University  800 Dongchuan Road Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guanlin","family":"Li","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Frontiers Science Center for Transformative Molecules School of Chemistry and Chemical Engineering Shanghai Jiao Tong University  800 Dongchuan Road Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7486-099X","authenticated-orcid":false,"given":"Xiaohong","family":"Huo","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Frontiers Science Center for Transformative Molecules School of Chemistry and Chemical Engineering Shanghai Jiao Tong University  800 Dongchuan Road Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4788-4195","authenticated-orcid":false,"given":"Wanbin","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Frontiers Science Center for Transformative Molecules School of Chemistry and Chemical Engineering Shanghai Jiao Tong University  800 Dongchuan Road Shanghai 200240 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,10,19]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1131943"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/B610213C"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr800221v"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm401375q"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00392"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00778"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1080\/17460441.2021.1933427"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed1003806"},{"key":"e_1_2_7_10_1","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1CS15241F"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ejmech.2019.111826"},{"key":"e_1_2_7_13_1","unstructured":"\u00a0"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol9902172"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.2165\/00128071-200102030-00009"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.nucmedbio.2020.02.006"},{"key":"e_1_2_7_17_1","unstructured":"\u00a0"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b04088"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b03989"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2013.06.004"},{"key":"e_1_2_7_21_1","unstructured":"For 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group:"},{"key":"e_1_2_7_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja209373k"},{"key":"e_1_2_7_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201403410"},{"key":"e_1_2_7_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol5000988"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr068410e"},{"key":"e_1_2_7_54_1","unstructured":"\u00a0"},{"key":"e_1_2_7_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9844229"},{"key":"e_1_2_7_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201209485"},{"key":"e_1_2_7_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c02150"},{"key":"e_1_2_7_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202307697"},{"key":"e_1_2_7_59_1","unstructured":"For the pioneering work on stereodivergent dual catalysis 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numbers2279253 [for (R S)-3\u2009lp] 2279251 [for (R R)-8] and 2279252 [for (S R)-9]contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_7_86_1","doi-asserted-by":"publisher","DOI":"10.1021\/om980840a"},{"key":"e_1_2_7_87_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.26812"},{"key":"e_1_2_7_88_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja300743t"},{"key":"e_1_2_7_89_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00031a008"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202313838","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,6,21]],"date-time":"2024-06-21T15:15:54Z","timestamp":1718982954000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202313838"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,10,19]]},"references-count":89,"journal-issue":{"issue":"47","published-print":{"date-parts":[[2023,11,20]]}},"alternative-id":["10.1002\/anie.202313838"],"URL":"https:\/\/doi.org\/10.1002\/anie.202313838","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,10,19]]},"assertion":[{"value":"2023-09-16","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-10-19","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202313838"}}