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We herein report a catalytic asymmetric trifluoromethylation of cyclic ketones via a Sc<jats:sup>III<\/jats:sup>\/chiral bisoxazoline\u2010catalyzed homologation reaction by employing 2,2,2\u2010trifluorodiazoethane (CF<jats:sub>3<\/jats:sub>CHN<jats:sub>2<\/jats:sub>) as the CF<jats:sub>3<\/jats:sub> source. This desymmetrization process is highly efficient and generates two chiral centers with excellent diastereoselectivity and enantioselectivity, affording chiral <jats:italic>\u03b1<\/jats:italic>\u2010trifluoromethyl cyclic ketones in a straightforward manner.<\/jats:p>","DOI":"10.1002\/anie.202115098","type":"journal-article","created":{"date-parts":[[2021,12,14]],"date-time":"2021-12-14T03:05:20Z","timestamp":1639451120000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":45,"title":["Catalytic Asymmetric Homologation of 4\u2010Substituted Cyclohexanones with CF<sub>3<\/sub>CHN<sub>2<\/sub>: Enantioselective Synthesis of \u03b1<i>\u2010<\/i>Trifluoromethyl Cycloheptanones"],"prefix":"10.1002","volume":"61","author":[{"given":"Shu\u2010Sen","family":"Li","sequence":"first","affiliation":[{"name":"Beijing National Laboratory of Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of 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