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Catalytic methods to provide direct access to aliphatic trifluoromethyl ketones are highly desirable yet remain underdeveloped, partially owing to the high reactivity and instability of trifluoroacetyl radical. Herein, we report a photocatalytic synthesis of trifluoromethyl ketones from alkyl bromides with trifluoroacetic anhydride. The reaction features dual visible\u2010light and halogen\u2010atom\u2010transfer catalysis, followed by an enabling radical\u2010radical cross\u2010coupling of an alkyl radical with a stabilized trifluoromethyl radical. The reaction provides straightforward access to aliphatic trifluoromethyl ketones from readily available and cost\u2010effective alkyl halides and trifluoroacetic anhydride (TFAA).<\/jats:p>","DOI":"10.1002\/anie.202308732","type":"journal-article","created":{"date-parts":[[2023,8,3]],"date-time":"2023-08-03T12:06:10Z","timestamp":1691064370000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":38,"title":["Access to Trifluoromethylketones from Alkyl Bromides and Trifluoroacetic Anhydride by Photocatalysis"],"prefix":"10.1002","volume":"62","author":[{"given":"Hai\u2010Wu","family":"Du","sequence":"first","affiliation":[{"name":"Shenzhen Grubbs Institute and Department of Chemistry Southern University of Science and Technology  Shenzhen 518055 Guangdong P. R. 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