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Herein, we report a tunable C\u2013C coupling strategy for the divergent synthesis of multisubstituted alkenes from alkenylsulfonium salts and cyanofluoromethyl phosphonate. The choice between t-BuOK and DBU as the base selectively furnishes either \u03b1-fluoro allylnitriles or the corresponding isomerized \u03b1-fluoro acrylonitriles. Remarkably, under DBU-promoted conditions, a one-pot incorporation of alcohols drives a tandem transesterification process, delivering diversified \u03b1-fluoro acrylonitriles with high regio- and stereocontrol. Furthermore, the synthetic utility of this method is further demonstrated by the late-stage modification of complex bioactive molecules and versatile product transformations.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c02821","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T14:02:35Z","timestamp":1785852155000},"page":"11194-11199","source":"Crossref","is-referenced-by-count":0,"title":["Base-Controlled Regioselective Synthesis of \u03b1-Fluoro-Allylnitriles\nand -Acrylonitriles from Alkenylsulfonium Salts and Cyanofluoromethyl\nPhosphonate"],"prefix":"10.1021","volume":"28","author":[{"given":"Xiang","family":"Wang","sequence":"first","affiliation":[{"name":"Shanghai University of Engineering Science , , 333 Longteng Road , ,","place":["Shanghai, China, 201620"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sanhua","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shanghai University of Engineering Science , , 333 Longteng Road , ,","place":["Shanghai, China, 201620"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6545-5087","authenticated-orcid":true,"given":"Youcan","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shanghai University of Engineering Science , , 333 Longteng Road , ,","place":["Shanghai, China, 201620"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-8198-0871","authenticated-orcid":true,"given":"Tiefeng","family":"Xu","sequence":"additional","affiliation":[{"name":"Zhejiang Sci-Tech University , , ,","place":["Hangzhou, China, 310018"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4356-7042","authenticated-orcid":true,"given":"Ya","family":"Li","sequence":"additional","affiliation":[{"name":"Shanghai University of Engineering Science , , 333 Longteng Road , ,","place":["Shanghai, China, 201620"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,31]]},"reference":[{"key":"2026091110063913800_cit1a","doi-asserted-by":"publisher","first-page":"3496","DOI":"10.1039\/c0cs00221f","article-title":"Organic fluorine compounds: a great\nopportunity for enhanced materials properties","volume":"40","author":"Berger","year":"2011","journal-title":"Chem. 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