Copper‐Catalyzed C(sp ³ )−H α‐Acetylation: Generation of Quaternary Centers

α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in natural products and pharmaceuticals. We report the α-acetylation of C(sp³)-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH₂R at RT with ^tBuOO^tBu as oxidant via copper(I) <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:semantics><mml:mi>β</mml:mi> <mml:annotation>${\beta }$</mml:annotation> </mml:semantics> </mml:math> -diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution 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^II](CH₂C(O)Ar) that capture alkyl radicals R• to give R-CH₂C(O)Ar outcompeting dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH₂CH₂C(O)Ar.