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In this approach, two haloalkyl radicals generated from chloroform via halogen atom transfer (XAT) and direct single electron transfer (SET) within the same photoredox catalysis cycle enable the 1,4\u2010dichloromethyldimerization of alkenes. Besides chloroform, this strategy is applicable to carbon tetrachloride, bromotrichloromethane, and \u03b1\u2010bromo carboxylic esters, yielding corresponding 1,4\u2010disubstituted vicinal diaryl alkanes. Diverse polychlorinated structures containing highly congested vicinal quaternary carbon centers are effectively synthesized by this method. The potential of this reaction in late\u2010stage drug modification is highlighted by the successful transformation of olefins with pharmaceutical structures.<\/jats:p>","DOI":"10.1002\/chem.202404389","type":"journal-article","created":{"date-parts":[[2025,1,5]],"date-time":"2025-01-05T22:38:22Z","timestamp":1736116702000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Photoredox\u2010Catalyzed 1,4\u2010Dichloromethyldimerization of Alkenes with Chloroform: Access to Polychlorinated Vicinal Diaryl Alkanes"],"prefix":"10.1002","volume":"31","author":[{"given":"Zhu\u2010Ming","family":"Qian","sequence":"first","affiliation":[{"name":"Key Laboratory of Applied Chemistry of Chongqing Municipality School of Chemistry and Chemical Engineering Southwest University  400715 Chongqing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ming\u2010Lin","family":"Yang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Applied Chemistry of Chongqing Municipality School of Chemistry and Chemical Engineering Southwest University  400715 Chongqing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhi","family":"Guan","sequence":"additional","affiliation":[{"name":"Key Laboratory of Applied Chemistry of Chongqing Municipality School of Chemistry and Chemical Engineering Southwest University  400715 Chongqing China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chu\u2010Sheng","family":"Huang","sequence":"additional","affiliation":[{"name":"Guangxi Key Laboratory of Natural Polymer Chemistry and Physics College of Chemistry and Materials Nanning Normal University  530001 Nanning P.\u2005R. 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