{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,12]],"date-time":"2025-12-12T13:49:13Z","timestamp":1765547353271,"version":"3.41.2"},"reference-count":82,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2025,1,3]],"date-time":"2025-01-03T00:00:00Z","timestamp":1735862400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100001341","name":"Richard and Susan Smith Family Foundation","doi-asserted-by":"publisher","award":["Excellence Award"],"award-info":[{"award-number":["Excellence Award"]}],"id":[{"id":"10.13039\/100001341","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":[[2025,3,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Sulfenyl fluorides are organic compounds of sulfur in formal oxidation state +2 with the formula R\u2212S\u2212F. Although the chloride, bromide, and iodide analogues have been extensively described in the literature, arenesulfenyl fluorides remain essentially unstudied. These structures have been implicated as putative intermediates in established processes to access polyfluorinated sulfur species; however, definitive and direct evidence of their existence has not been obtained, nor has a systematic understanding of their reactivity. Here, we report the synthesis, isolation, and spectroscopic characterization of several arenesulfenyl fluorides, including structural analysis of 2,4\u2010dinitrobenzenesulfenyl fluoride and 4\u2010cyano\u20102\u2010nitrobenzenesulfenyl fluoride by single\u2010crystal X\u2010ray diffraction. The functional group undergoes direct, efficient, and highly regioselective <jats:italic>anti<\/jats:italic>\u2010addition to alkenes and alkynes, as well as insertion by carbenes. The resulting \u03b1\u2010 or \u03b2\u2010fluoro thioether adducts can be readily transformed into useful fluorinated motifs, for example by modification of the sulfur groups (to sulfonamides or sulfonyl fluorides), by sulfur elimination (to generate formal C\u2212H fluorination products), or by Julia\u2013Kocienski olefination (to form vinyl fluorides). Thus, we establish that sulfenyl fluorides are unexpectedly accessible and stable compounds, which serve as versatile reagents for the production of fluorinated organic compounds.<\/jats:p>","DOI":"10.1002\/anie.202422120","type":"journal-article","created":{"date-parts":[[2024,12,13]],"date-time":"2024-12-13T19:30:03Z","timestamp":1734118203000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Synthesis of Arenesulfenyl Fluorides and Fluorosulfenylation of Alkenes, Alkynes, and \u03b1\u2010Diazocarbonyl Compounds"],"prefix":"10.1002","volume":"64","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6149-3406","authenticated-orcid":false,"given":"Nathan H.","family":"Faialaga","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Biology Harvard University Cambridge  Massachusetts 02138 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6336-1899","authenticated-orcid":false,"given":"Dana P.","family":"Gephart","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Harvard University Cambridge  Massachusetts 02138 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-3335-8678","authenticated-orcid":false,"given":"Breno D.","family":"Silva","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Harvard University Cambridge  Massachusetts 02138 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0951-6487","authenticated-orcid":false,"given":"Richard Y.","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Harvard University Cambridge  Massachusetts 02138 United States"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,1,3]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.191104401109"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/jlac.19123910106"},{"key":"e_1_2_8_3_1","unstructured":"G. Zel\u010dans T.\u2005K. Hutton R. Rios N. Shibata inEncyclopedia of Reagents for Organic Synthesis(Ed.: John Wiley & Sons Ltd) John Wiley & Sons Ltd Chichester UK 2013 p. rb019.pub3."},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1055\/s-1970-21640"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00271F"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01197a009"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01133a510"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01593a030"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)81343-X"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1978.951"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.15227\/orgsyn.044.0047"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr60123a004"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19120450323"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2009.1188"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/a805449e"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cdc.2019.100186"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(00)84082-8"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19804690120"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19784390122"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500336u"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01502a083"},{"key":"e_1_2_8_22_1","doi-asserted-by":"crossref","unstructured":"F. 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Nauk SSSR Seriya Khimischeskikh Nauk1972 14 78\u201388."},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF00854656"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(00)83114-0"},{"key":"e_1_2_8_35_1","unstructured":"Furin reports as19F chemical shifts for pentafluorobenzenesulfenyl fluoride: +4.1 (claimed S\u2212F) \u2212144.7 \u2212146.2 \u2212160.8\u2005ppm (adjusted for the modern sign convention and reference). These data are consistent with instead a sulfinyl fluoride: +6.1 (SO\u2212F) \u2212142.8 \u2212146.4 \u2212158.8\u2005ppm as reported inJ. Fluor. Chem.1972 2 53\u201361. DFT (B97D\/6-311+G(d p\/SMD(THF)) estimates the sulfur-bound fluorine nucleus to be at a chemical shift of \u2212383.5\u2005ppm."},{"key":"e_1_2_8_36_1","doi-asserted-by":"crossref","unstructured":"A. Haas U. 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Adcock R.\u2005E. Banks A. Bulan J. Burdon K.\u2005O. Christe W. Dmowski G.\u2005G. Furin U. Gro\u00df D. Hage G.\u2005B. Hammond M.\u2005M. Kremlev R.\u2005J. Lagow B. Langlois D. Meshri R. Miethchen R. Perry D. Peters K. Pohmer R.\u2005L. Powell M.\u2005H. Rock S. Rozen St. R\u00fcdiger G. Siegemund J. St\u00f6lting L.\u2005R. Subramanian J.\u2005C. Tatlow T. Tojo K. Ulm N. Watanabe L.\u2005M. Yagupolskii L. Yu M. Zupan inOrgano-Fluorine Compounds Thieme Verlag Stuttgart 1998."},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.5b02075"},{"key":"e_1_2_8_62_1","unstructured":"FTIR spectroscopy of arenesulfenyl fluorides1\u2009b 3a and3brevealed signals at 656 660 and 659\u2005cm\u22121respectively. 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