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While binary electron donor\u2013acceptor systems have been extensively explored, the catalytic potential of higher-order multicomponent charge-transfer complexes remains largely underdeveloped. Here we report a distinct ternary charge-transfer complex formed by noncovalent interactions of \u03b1-bromo-substituted alkyl electrophiles, silyl enol ether, and o-phenylenediamine, which drives the formation of the \u03b1-carbon radical upon visible-light irradiation to establish a chain process. This transformation enables the efficient and modular construction of highly substituted furans and diverse \u03b1-alkylated ketones under mild conditions. These findings underscore the untapped potential of simple organic molecules to mediate photochemical transformations through an unconventional multicomponent charge-transfer process.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03005","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T19:04:41Z","timestamp":1788462281000},"page":"11481-11488","source":"Crossref","is-referenced-by-count":0,"title":["Modular Assembly\nof Multisubstituted Furans and \u03b1-Alkylated\nKetones via Photoactivation of Aniline-Linked Ternary Charge-Transfer\nComplexes"],"prefix":"10.1021","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-4648-6223","authenticated-orcid":true,"given":"Minyu","family":"Yang","sequence":"first","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 100049"]},{"name":"Sun Yat-sen University , , ,","place":["Guangzhou, China, 510006"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shao-Fei","family":"Ni","sequence":"additional","affiliation":[{"name":"Shantou University , , ,","place":["Shantou, China, 515063"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dong","family":"Li","sequence":"additional","affiliation":[{"name":"Shantou University , , ,","place":["Shantou, China, 515063"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaozhuo","family":"Xu","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zunaira","family":"Riffat","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Djike Tchuente Berol","family":"Loik","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hang","family":"Gu","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9065-112X","authenticated-orcid":true,"given":"Yaping","family":"Shang","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5695-6333","authenticated-orcid":true,"given":"Weiping","family":"Su","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Fuzhou, China, 350108"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,7]]},"reference":[{"key":"2026091809412455100_cit1a","doi-asserted-by":"publisher","first-page":"5322","DOI":"10.1021\/cr300503r","article-title":"Visible\nLight Photoredox Catalysis with Transition Metal Complexes: Applications\nin Organic Synthesis","volume":"113","author":"Prier","year":"2013","journal-title":"Chem. 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J."},{"key":"2026091809412455100_cit13a","doi-asserted-by":"publisher","first-page":"5704","DOI":"10.1021\/acs.orglett.6b02869","article-title":"Synthesis of 1,4-Dicarbonyl Compounds from Silyl Enol\nEthers and Bromocarbonyls, Catalyzed by an Organic Dye under Visible-Light\nIrradiation with Perfect Selectivity for the Halide Moiety over the\nCarbonyl Group","volume":"18","author":"Esumi","year":"2016","journal-title":"Org. Lett."},{"key":"2026091809412455100_cit13b","doi-asserted-by":"publisher","first-page":"414","DOI":"10.1002\/ajoc.201600489","article-title":"Synthesis of Tetrasubstituted Furans\nby Using Photoredox-Catalyzed Coupling of 2-Bromo-1,3-dicarbonyl Compounds\nwith Silyl Enol Ethers","volume":"6","author":"Han","year":"2017","journal-title":"Asian J. Org. 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Chem."},{"key":"2026091809412455100_cit18a","doi-asserted-by":"publisher","first-page":"1336","DOI":"10.1055\/s-0036-1558970","article-title":"Mechanochemical\nGrinding Diels-Alder Reaction: Highly Efficient and Rapid Access to\nBi-, Tri-, and Tetracyclic Systems","volume":"28","author":"Peddinti","year":"2017","journal-title":"Synlett"},{"key":"2026091809412455100_cit18b","doi-asserted-by":"publisher","first-page":"1926","DOI":"10.1002\/1521-3773(20010518)40:10&lt;1926::AID-ANIE1926&gt;3.0.CO;2-3","article-title":"Solid-State\nIsomerization of Stropodiastereomers: Effective Diastereoselection\nthrough Polymorphic Transformations","volume":"40","author":"Einhorn","year":"2001","journal-title":"Angew.\nChem., Int. 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Ed."},{"key":"2026091809412455100_cit21","doi-asserted-by":"publisher","first-page":"9485","DOI":"10.1002\/anie.201915814","article-title":"A Photochemical\nOrganocatalytic Strategy for the \u03b1-Alkylation\nof Ketones by Using Radicals","volume":"59","author":"Spinnato","year":"2020","journal-title":"Angew. Chem.,\nInt. Ed."},{"issue":"6","key":"2026091809412455100_cit22","doi-asserted-by":"publisher","first-page":"693","DOI":"10.1246\/cl.1985.693","article-title":"Nouvelle Synthese de Furannes","volume":"14","author":"Duhamel","year":"1985","journal-title":"Chem. Lett."},{"issue":"11","key":"2026091809412455100_cit23","doi-asserted-by":"publisher","first-page":"1546","DOI":"10.1002\/ajoc.201700340","article-title":"Paal-Knorr Furan Synthesis Using\nTiCl4 as Dehydrating Agent: a Concise Furan Synthesis from \u03b1-Haloketones and \u03b2-Dicarbonyl\nCompounds","volume":"6","author":"Luo","year":"2017","journal-title":"Asian J. Org. Chem."},{"key":"2026091809412455100_cit24a","doi-asserted-by":"publisher","first-page":"5426","DOI":"10.1039\/C5SC02185E","article-title":"Characterizing Chain\nProcesses in Visible Light Photoredox Catalysis","volume":"6","author":"Cismesia","year":"2015","journal-title":"Chem. Sci."},{"key":"2026091809412455100_cit24b","doi-asserted-by":"publisher","first-page":"1569","DOI":"10.1039\/D2SC05973H","article-title":"Coupling of \u03b1-Bromoamides and Unactivated Alkenes to Form \u03b3-Lactams through EDA and Photocatalysis","volume":"14","author":"Treacy","year":"2023","journal-title":"Chem.\nSci."},{"key":"2026091809412455100_cit25","doi-asserted-by":"publisher","first-page":"4092","DOI":"10.1021\/acs.orglett.9b01275","article-title":"Visible-Light Photocatalytic Preparation\nof 1,4-Ketoaldehydes and 1,4-Diketones from \u03b1-Bromoketones and Alkyl Enol Ethers","volume":"21","author":"Garci\u0301a-Santos","year":"2019","journal-title":"Org. 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