Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Июнь 4, 2025
Reductive elimination of dialkyl Ni(II) species for the enantioselective construction a C(sp3)-C(sp3) bond represents fundamental challenge due to low oxidative ability ion. Here we report that Ni(0) complex can perform as π-Lewis base activate 2,4-dienoic carboxylate salts formed in situ with zinc reagents, such dimethylzinc, and undergo vinylogous addition carbonyls α-regioselectively stereoselectively. After transmetalation another organometallic reagent, resultant alkyl allylic nickel(II) readily undertake reductive finally forge two bonds, even switchable diastereodivergence α,β- or α,δ-regiodivergence via ligand substrate control. A self-assembled dinuclear Zn cage framework is believed enhance latter process through an intriguing outer-sphere π-acidic activation mode.
Язык: Английский