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Herein, we report a transition-metal-free, stereoselective defluorinative thiolation of gem-difluoroalkenes with thiols under simple base promotion. This transformation proceeds efficiently through a nucleophilic substitution pathway, affording a broad array of monofluoroalkenyl sulfides in generally good yields with excellent stereoselectivities (Z\/E up to 24:1). This protocol features a broad substrate scope and excellent functional group tolerance, representing a convenient approach to stereodefined monofluoroalkenyl sulfides.<\/jats:p>","DOI":"10.1021\/acs.joc.6c01159","type":"journal-article","created":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T20:02:13Z","timestamp":1791921733000},"page":"13983-13989","source":"Crossref","is-referenced-by-count":0,"title":["Stereoselective Defluorinative Thiolation of\n                    <i>gem<\/i>\n                    -Difluoroalkenes with Thiols via Nucleophilic Substitution"],"prefix":"10.1021","volume":"91","author":[{"given":"Xin","family":"Guo","sequence":"first","affiliation":[{"name":"Zunyi Medical University , , ,","place":["Zunyi, P.R. China, 563003"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dandan","family":"Xia","sequence":"additional","affiliation":[{"name":"Zunyi Medical University , , ,","place":["Zunyi, P.R. 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