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Herein, we show that the transferred product further undergoes a skeletal transformation on silica gel. The transformation begins with activation of the allylic C\u2212F bond on the silanol surface. Then, the resulting carbocation readily undergoes a regioselective nucleophilic aromatic substitution with water, depending on the position of the fluorine substituents. Hexafluoro\u20102\u2010propanol also activated the allylic C\u2212F bond and acted as a nucleophile. These findings support the generation of a highly reactive cationic electrophilic intermediate in the successive transformations involving fluorine atoms.<\/jats:p>","DOI":"10.1002\/chem.202200132","type":"journal-article","created":{"date-parts":[[2022,2,16]],"date-time":"2022-02-16T23:04:43Z","timestamp":1645052683000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Skeletal Transformation Triggered by C\u2212F Bond Activation after Photochemical Rearrangement of Fluorinated [7]Helicenes"],"prefix":"10.1002","volume":"28","author":[{"given":"Chikako","family":"Matsuda","sequence":"first","affiliation":[{"name":"Faculty of Science Yamagata University  1-4-12 Kojirakawa-machi Yamagata Yamagata 990-8560 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryo","family":"Igarashi","sequence":"additional","affiliation":[{"name":"Faculty of Science Yamagata University  1-4-12 Kojirakawa-machi Yamagata Yamagata 990-8560 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4100-9995","authenticated-orcid":false,"given":"Hiroshi","family":"Katagiri","sequence":"additional","affiliation":[{"name":"Graduate School of Science and Engineering Yamagata University  4-3-16 Jonan Yonezawa Yamagata 992-8510 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7811-1734","authenticated-orcid":false,"given":"Takashi","family":"Murase","sequence":"additional","affiliation":[{"name":"Faculty of Science Yamagata University  1-4-12 Kojirakawa-machi Yamagata Yamagata 990-8560 Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,3,4]]},"reference":[{"key":"e_1_2_8_1_1","unstructured":"For selected reviews on helicenes see:"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.197406491"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1007\/3-540-13569-3_3"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr200087r"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35154D"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35111K"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35134J"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochemrev.2013.11.001"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00620A"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-662-53168-6"},{"key":"e_1_2_8_11_1","unstructured":"\u00a0"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19750580314"},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo048707h"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2011.12.082"},{"key":"e_1_2_8_15_2","doi-asserted-by":"publisher","DOI":"10.1039\/C3CC46986G"},{"key":"e_1_2_8_16_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2662"},{"key":"e_1_2_8_17_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-22992-6"},{"key":"e_1_2_8_18_1","unstructured":"\u00a0"},{"key":"e_1_2_8_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/jr9650005920"},{"key":"e_1_2_8_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp401629k"},{"key":"e_1_2_8_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201404877"},{"key":"e_1_2_8_22_1","unstructured":"\u00a0"},{"key":"e_1_2_8_23_2","doi-asserted-by":"publisher","DOI":"10.1038\/s42004-018-0099-7"},{"key":"e_1_2_8_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202001295"},{"key":"e_1_2_8_25_1","unstructured":"\u00a0"},{"key":"e_1_2_8_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00152a022"},{"key":"e_1_2_8_27_2","doi-asserted-by":"publisher","DOI":"10.1002\/bscb.19850940309"},{"key":"e_1_2_8_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo0506231"},{"key":"e_1_2_8_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201000374"},{"key":"e_1_2_8_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201502473"},{"key":"e_1_2_8_31_2","doi-asserted-by":"publisher","DOI":"10.3390\/cryst7080251"},{"key":"e_1_2_8_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CP07552E"},{"key":"e_1_2_8_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.8b02870"},{"key":"e_1_2_8_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.202000037"},{"key":"e_1_2_8_35_1","unstructured":"An unusual fluorine atom rearrangement occurs in the oxidative photocyclization of 1-fluoro[5]helicene. 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