Nickel/Photoredox Dual-Catalyzed, Regioselective 1,2-Carboacylation of Alkenes via Synergistic Alkyl and Benzoyl Radical Coupling

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 2, 2025

A regioselective 1,2-carboacylation protocol of alkenes via nickel/photoredox dual catalysis has been successfully developed under mild conditions. wide range alkyl bromides, α-oxocarboxylic acids, and styrenes proved to be compatible the optimized conditions, affording corresponding products in up 91% yields. Mechanistically, key success this approach is temporal orchestration radical generation: nickel-catalyzed halogen atom transfer (XAT) for bromides photoredox-driven decarboxylation acids.

Язык: Английский

Divergent Asymmetric Dialkylation of Dienoic Acids with Carbonyls and Zinc Reagents via Tandem Ni(0) and Ni(II) Catalysis

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