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We report the \u03b1\u2010acetylation of C(sp\n                    <jats:sup>3<\/jats:sup>\n                    )\u2212H substrates R\u2212H with arylmethyl ketones ArC(O)Me to provide \u03b1\u2010alkylated ketones ArC(O)CH\n                    <jats:sub>2<\/jats:sub>\n                    R at RT with\n                    <jats:sup>t<\/jats:sup>\n                    BuOO\n                    <jats:sup>t<\/jats:sup>\n                    Bu as oxidant via copper(I) \n\u2010diketiminato catalysts. Proceeding via alkyl radicals R\u2022, this method enables \u03b1\u2010substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu\n                    <jats:sup>II<\/jats:sup>\n                    ](CH\n                    <jats:sub>2<\/jats:sub>\n                    C(O)Ar) that capture alkyl radicals R\u2022 to give R\u2212CH\n                    <jats:sub>2<\/jats:sub>\n                    C(O)Ar outcompeting dimerization of the copper(II) enolate to give the 1,4\u2010diketone ArC(O)CH\n                    <jats:sub>2<\/jats:sub>\n                    CH\n                    <jats:sub>2<\/jats:sub>\n                    C(O)Ar.\n                  <\/jats:p>","DOI":"10.1002\/anie.202418692","type":"journal-article","created":{"date-parts":[[2024,10,31]],"date-time":"2024-10-31T00:10:03Z","timestamp":1730333403000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Copper\u2010Catalyzed C(sp\n                    <sup>3<\/sup>\n                    )\u2212H \u03b1\u2010Acetylation: Generation of Quaternary Centers"],"prefix":"10.1002","volume":"64","author":[{"given":"Otome E.","family":"Okoromoba","sequence":"first","affiliation":[{"name":"Department of Chemistry Georgetown University  Box 571227 20057-1227 Washington DC USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ting\u2010An","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Chemistry Georgetown University  Box 571227 20057-1227 Washington DC USA"},{"name":"Department of Chemistry Michigan State University  578 S. 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