Asymmetric Multi-Atom Insertion of Esters via Rh-Catalyzed Ring Opening of Oxabicyclic Alkenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Precise skeletal manipulation involving insertion, deletion, and replacement has garnered considerable attention within the synthetic chemistry community. Among these processes, multi-atom insertion reactions in acyclic compounds remain a formidable challenge, primarily due to low efficiency of fragment recapture after cleavage, which results from lack substrate-specific proximity during reconstruction stage. Here, we report an asymmetric reaction esters via Rh-catalyzed ring opening oxabicyclic alkenes, achieving excellent regio-, diastereo-, enantioselectivity. This approach enables efficient rapid construction molecular library with chiral hydroxy-dihydronaphthalene scaffold, showcasing atom-efficient reaction. Detailed density functional theory calculations reveal key mechanistic features stereoselectivity-determining model this transformation.

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