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In the context of converting helicenes into planar coronenes, tetrafluorinated thia[6]helicene <jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>\u2010dioxide undergoes a smooth intramolecular Diels\u2013Alder reaction to afford the difluorinated coronene. However, the corresponding <jats:italic>S<\/jats:italic>\u2010oxide counterpart is affected by competing side reactions that limit its utility. Herein, we demonstrate that introducing a trimethylsilyl (TMS) group onto the thiophene <jats:italic>S<\/jats:italic>\u2010oxide ring suppresses self\u2010condensation and enables more efficient coronene conversion than its <jats:italic>S<\/jats:italic>,<jats:italic>S<\/jats:italic>\u2010dioxide counterpart. Unexpectedly, the TMS group is removed during the transformation, yielding both the TMS\u2010protected and deprotected forms of the difluorinated coronene. Mechanistic investigations suggest that this desilylation arises from the combined effect of Si\u00b7\u00b7\u00b7F interactions and in\u2010situ\u2010generated sulfur monoxide (SO). These findings provide insights into the reactivity control of thiophene <jats:italic>S<\/jats:italic>\u2010oxides and demonstrate how silicon, fluorine, and SO can influence cascade transformations toward functionalized polycyclic aromatic systems.<\/jats:p>","DOI":"10.1002\/chem.202502242","type":"journal-article","created":{"date-parts":[[2025,8,26]],"date-time":"2025-08-26T06:53:09Z","timestamp":1756191189000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Transformation of Silyl\u2010Protected Tetrafluorinated Thia[6]helicene S\u2010Oxide into a Difluorinated Coronene via Induced Desilylation"],"prefix":"10.1002","volume":"31","author":[{"given":"Ayumu","family":"Nakao","sequence":"first","affiliation":[{"name":"Faculty of Science Yamagata University 1\u20104\u201012 Kojirakawa\u2010machi Yamagata 990\u20108560 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4100-9995","authenticated-orcid":false,"given":"Hiroshi","family":"Katagiri","sequence":"additional","affiliation":[{"name":"Graduate School of Organic Materials Science Yamagata University 4\u20103\u201016 Jonan Yonezawa 992\u20108510 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7811-1734","authenticated-orcid":false,"given":"Takashi","family":"Murase","sequence":"additional","affiliation":[{"name":"Faculty of Science Yamagata University 1\u20104\u201012 Kojirakawa\u2010machi Yamagata 990\u20108560 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,8,25]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr200087r"},{"key":"e_1_2_9_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35154D"},{"key":"e_1_2_9_1_3","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-662-53168-6"},{"key":"e_1_2_9_1_4","doi-asserted-by":"publisher","DOI":"10.1002\/9783527829415"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19750580314"},{"key":"e_1_2_9_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo048707h"},{"key":"e_1_2_9_2_3","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2011.12.082"},{"key":"e_1_2_9_2_4","doi-asserted-by":"publisher","DOI":"10.1039\/C3CC46986G"},{"key":"e_1_2_9_2_5","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2662"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s42004-018-0099-7"},{"key":"e_1_2_9_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202001295"},{"key":"e_1_2_9_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202200132"},{"key":"e_1_2_9_4_1","first-page":"51","volume-title":"Organic Reactions","author":"Mallory F. 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