Recent Progress in Transition-Metal-Catalyzed Reductive Cross-Coupling Reactions Using Diboron Reagents as Reductants

ACS Catalysis, Год журнала: 2023, Номер 13(23), С. 15469 - 15480

Опубликована: Ноя. 16, 2023

Transition-metal-catalyzed reductive cross-coupling reactions have been developed as one of the important tools for constructing C–C bonds. These involve direct coupling two distinct electrophiles promoted by transition metals and reductants. Notably, these methods offer advantages over conventional because they circumvent need air- moisture-sensitive organometallic reagents while being simple to operate exhibiting good compatibility with various functional groups. In recent years, diboron gained prominence reductants alongside traditional metal reductants, such Zn, Mn, Mg. This Review aims provide an insightful overview nickel/copper/iron-catalyzed using illustrate their possible reaction mechanisms.

Язык: Английский

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Transition metal-catalyzed asymmetric three-component dicarbofunctionalization of unactivated alkenes

Chem Catalysis, Год журнала: 2023, Номер 3(9), С. 100690 - 100690

Опубликована: Июль 13, 2023

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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Nickel-Catalyzed Cross-Electrophile Ring Opening/gem-Difluoroallylation of Aziridines

Organic Letters, Год журнала: 2023, Номер 25(31), С. 5756 - 5761

Опубликована: Июль 28, 2023

Herein we report a nickel-catalyzed regioselective cross-electrophile ring opening reaction of sulfonyl-protected aziridines with trifluoromethyl-substituted alkenes as the gem-difluoroallylating agents, providing new and efficient entry to prepare gem-difluorobishomoallylic sulfonamides. Moreover, scaffold 6-fluoro-1,2,3,4-tetrahydropyridine can be constructed starting from products via NaH-mediated intramolecular defluorinative nucleophilic vinylic substitution.

Язык: Английский

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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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Nickel-catalyzed electrophiles-controlled enantioselective reductive arylative cyclization and enantiospecific reductive alkylative cyclization of 1,6-enynes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 27, 2024

Transition metal-catalyzed asymmetric cyclization of 1,6-enynes is a powerful tool for the construction chiral nitrogen-containing heterocycles. Despite notable achievements, these transformations have been largely limited to use aryl or alkenyl metal reagents, and stereoselective stereospecific alkylative remains unexploited. Herein, we report Ni-catalyzed enantioselective reductive anti-arylative with iodides, providing enantioenriched six-membered carbo- heterocycles in good yields excellent enantioselectivities. Additionally, realized enantiospecific cis-alkylative alkyl bromides, furnishing five-membered high regioselectivity stereochemical fidelity. Mechanistic studies reveal that arylative initiated by oxidative addition Ni(0) halides triggered allylic acetates. The utility this strategy further demonstrated synthesis antiepileptic drug Brivaracetam.

Язык: Английский

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NMR spectroscopic investigations of transition metal complexes in organometallic and bioinorganic chemistry

Bulletin of the Korean Chemical Society, Год журнала: 2024, Номер 45(7), С. 593 - 613

Опубликована: Май 28, 2024

Abstract The field of coordination chemistry has evolved to intersect with organic and biochemistry, giving rise the disciplines organometallic bioinorganic chemistry. Nuclear magnetic resonance (NMR) spectroscopy can be applied for characterizing transition metal complexes, spanning both diamagnetic paramagnetic complexes prevalent in compounds metalloproteins. This review offers a comprehensive overview wide variety characterization techniques, ranging from basic 1 H 13 C NMR advanced methods such as heteronuclear experiments, polarization transfer relaxometry, multidimensional spectroscopy. diverse array spectroscopic outlined here promises enhance our comprehension facilitating development innovative catalysts therapeutics.

Язык: Английский

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Nickel-Catalyzed Enantioselective C(sp³)–C(sp³) Cross-Electrophile Coupling of N-Sulfonyl Styrenyl Aziridines with Alkyl Bromides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(37), С. 25426 - 25432

Опубликована: Сен. 4, 2024

Herein, we report the first example of a highly enantioselective alkylative aziridine ring opening. Under catalysis chiral nickel/pyridine-imidazoline complex, asymmetric C(sp

Язык: Английский

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P,N Ligand in Ni-Catalyzed Cross-Coupling Reactions: A Promising Tool for π-Functionalization

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13540 - 13560

Опубликована: Окт. 6, 2023

Bidentate P,N ligands, integrating phosphine and nitrogen donors, are highlighted for their versatile characteristics, offering both electronic steric tunability. Their hemilabile nature, coupled with the ability to modulate properties through choice of donor atoms substituents, has expanded horizons chemical transformations. This Review focuses on Ni-catalyzed cross-coupling reactions mediated by ligands. The asymmetrical nature each atom playing a specific role in catalytic cycle, offers control, stability, unique regioselectivity processes. In particular, Ni/P,N-catalytic system exhibits remarkable reactivity π-substrates including alkenes, alkynes, allenes. A thorough mechanistic understanding these processes insights into trends future directions Ni/P,N-catalyzed reactions.

Язык: Английский

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Diastereo- and Enantioselective Dearomative Reductive Aryl-Fluoroalkenylation of Indoles by Nickel Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6432 - 6439

Опубликована: Апрель 11, 2024

Herein, we disclose a nickel-catalyzed dearomative reductive aryl-fluoroalkenylation of indoles by defluorinative coupling with gem-difluoroalkenes. The catalytic protocol affords facile assembly various monofluoroalkene-containing polycyclic fused indolines bearing two contiguous carbon stereocenters in high diastereo- and enantioselectivities tolerance diverse functional groups.

Язык: Английский

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