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Under visible\u2010light energy transfer (\n                    <jats:sup>VL<\/jats:sup>\n                    EnT) catalysis, monosubstituted olefins react with octafluoronaphthalene to give dual dearomative ortho [2+2] cycloadducts selectively. In comparison, 1,1\u2010disubstituted olefins afford the corresponding para [4+2] cycloadducts with complete regiospecificity under otherwise identical conditions. Trisubstituted olefins engage in a diastereoconvergent [4+2] cycloaddition, delivering a single diastereomeric product regardless of the olefin geometry. This mild, operationally simple strategy provides direct access to structurally diverse, perfluorinated three\u2010dimensional molecular scaffolds, frameworks of increasing importance in drug discovery and materials science, from readily available starting materials in a single synthetic step. Control experiments and density functional theory calculations elucidated the\n                    <jats:sup>VL<\/jats:sup>\n                    EnT catalysis and olefin\u2010substitution\u2010controlled switching between distinct dearomative cycloaddition modes.\n                  <\/jats:p>","DOI":"10.1002\/anie.1846299","type":"journal-article","created":{"date-parts":[[2026,6,13]],"date-time":"2026-06-13T16:42:16Z","timestamp":1781368936000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Substrate\u2010Controlled Dearomative Cycloadditions of Perfluoronaphthalenes via Visible\u2010Light Energy Transfer Catalysis: Switchable Access to [2+2], [4+2], and Diastereoconvergent Cycloadducts"],"prefix":"10.1002","volume":"65","author":[{"given":"Sayan K.","family":"Jana","sequence":"first","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research Kolkata  Mohanpur West Bengal India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sanat Kumar","family":"Mahapatra","sequence":"additional","affiliation":[{"name":"Institute of Chemical Technology Mumbai\u2013IOC Odisha Campus Bhubaneswar Bhubaneswar India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sujay","family":"Dewan","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research Kolkata  Mohanpur West Bengal India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-6131-8260","authenticated-orcid":false,"given":"Biswajit","family":"Dutta","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research Kolkata  Mohanpur West Bengal India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pramod","family":"Rai","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research Kolkata  Mohanpur West Bengal India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4205-1626","authenticated-orcid":false,"given":"Lisa","family":"Roy","sequence":"additional","affiliation":[{"name":"Department of Education Indian Institute of Technology Kharagpur  Kharagpur India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5034-423X","authenticated-orcid":false,"given":"Biplab","family":"Maji","sequence":"additional","affiliation":[{"name":"Department of Chemical Sciences Indian Institute of Science Education and Research Kolkata  Mohanpur West Bengal India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,6,13]]},"reference":[{"key":"e_1_2_7_2_1","volume-title":"Asymmetric Catalysis in Organic Synthesis","author":"Noyori R.","year":"1994"},{"key":"e_1_2_7_3_1","volume-title":"Enantioselective Chemical Synthesis","author":"Corey E. 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