Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16753 - 16763

Опубликована: Июнь 11, 2024

In the realm of organic synthesis, catalytic and stereoselective formation C-glycosidic bonds is a pivotal process, bridging carbohydrates with aglycones. However, inherent chirality saccharide scaffold often has substantial impact on stereoinduction imposed by chiral ligand. this study, we have established an unprecedented zirconaaziridine-mediated asymmetric nickel catalysis, enabling diastereoselective coupling bench-stable glycosyl phosphates range (hetero)aromatic glycal iodides as feasible electrophiles. Our developed method showcases broad scope high tolerance for various functional groups. More importantly, precise stereocontrol toward both anomeric configurations forming C(sp2)-glycosides can be realized simply utilizing popular bioxazoline (biOx) ligands in reductive Ni catalysis. Regarding operating mechanism, experimental computational studies support occurrence redox transmetalation leading to transient, bimetallic Ni–Zr species that acts potent efficient single-electron reductant process.

Язык: Английский

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Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

ACS Catalysis, Год журнала: 2023, Номер 13(11), С. 7263 - 7268

Опубликована: Май 15, 2023

While being among the most common functional handles present in organic molecules, amines are a widely underutilized linchpin for C–C bond formation. To facilitate C–N cleavage, large activating groups typically used but result generation of stoichiometric amounts waste. Herein, we report an atom-economical activation benzylic primary relying on sulfur(VI) fluoride exchange (SuFEx) click chemistry and aza-Ramberg–Bäcklund reaction. This two-step sequence allows high-yielding 1,2-dialkyldiazenes from via loss SO2. Excitation diazenes with blue light Ir photocatalyst afford radical pairs upon expulsion N2, which can be coaxed into formation C(sp3)–C(sp2) bonds diffusion capture by Ni catalyst. arylative strategy traceless approach was harnessed variety examples, its mechanism investigated.

Язык: Английский

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Enantioselective Ni‐Catalyzed Three‐Component Dicarbofunctionalization of Alkenes

ChemCatChem, Год журнала: 2023, Номер 15(18)

Опубликована: Авг. 3, 2023

Abstract Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization alkenes has been well developed in recent years, which is used the area total synthesis natural products late‐stage modification drugs rapid incorporation sp 3 ‐enriched carbon centers. In this concept, significant breakthroughs field summarized, together with related mechanisms. Moreover, remaining challenges potential opportunities also highlighted.

Язык: Английский

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Ligand Relay for Nickel‐Catalyzed Decarbonylative Alkylation of Aroyl Chlorides

Advanced Science, Год журнала: 2023, Номер 11(9)

Опубликована: Дек. 13, 2023

Abstract Transition metal‐catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late‐stage applications. The development selective decarbonylative acid derivatives, most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable meaningful, but remains challenging. Herein, a strategy nickel‐catalyzed alkylation chlorides via phosphine/nitrogen ligand relay reported. simple phosphine found essential decarbonylation step, while nitrogen promotes cross‐electrophile coupling. Such system can effectively orderly carry out catalytic process at room temperature, utilizing easily available as an aryl electrophile reductive alkylation. This discovery provides new coupling, features operationally simple, conditions, excellent functional group tolerance. approach applied to methylation various pharmaceuticals. Extensive experiments are carried provide insights into reaction pathway support process.

Язык: Английский

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Nickel-catalyzed reductive formylation of aryl halides via formyl radical

Chinese Chemical Letters, Год журнала: 2024, Номер 35(12), С. 109783 - 109783

Опубликована: Март 20, 2024

Язык: Английский

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