Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis

ACS Catalysis, Год журнала: 2024, Номер 14(20), С. 15790 - 15798

Опубликована: Окт. 10, 2024

Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.

Язык: Английский

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Nickel‐Catalyzed Electrochemical Cross‐Electrophile C(sp2)‐C(sp3) Coupling via a NiII Aryl Amido Intermediate

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Июнь 8, 2024

Abstract Cross‐electrophile coupling (XEC) between aryl halides and alkyl is a streamlined approach for C(sp 2 )−C(sp 3 ) bond construction, which highly valuable in medicinal chemistry. Based on key Ni II amido intermediate, we developed selective scalable Ni‐catalyzed electrochemical XEC reaction (hetero)aryl primary secondary halides. Experimental computational mechanistic studies indicate that an amine ligand slows down the oxidative addition process of Ni‐polypyridine catalyst to bromide intermediate formed situ during process. The relatively slow beneficial enhancing selectivity reaction. stabilizes –aryl species prevent aryl–aryl homo‐coupling side reactions acts as activate substrates. This electrosynthesis system provides facile, practical, platform formation (hetero)aryl–alkyl bonds using standard catalysts under mild conditions. insights from this work could serve great foundation future cross‐couplings.

Язык: Английский

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Ni-catalyzed enantioselective three-component reductive alkylacylation of alkenes: modular access to structurally complex α-amino ketones

Chemical Science, Год журнала: 2024, Номер 15(37), С. 15489 - 15495

Опубликована: Янв. 1, 2024

Nickel-catalyzed three-component reductive dicarbofunctionalization of activated olefins (enamides) is presented.

Язык: Английский

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Accelerating stereoselective radical cross-couplings

Nature Chemistry, Год журнала: 2025, Номер 17(1), С. 8 - 10

Опубликована: Янв. 1, 2025

Язык: Английский

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Ni-catalyzed cross-electrophile alkyl-alkyl coupling reactions

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Язык: Английский

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Pyridine vs. Thiazole in Cyclometalated N^C^N Ni(II) Complexes

Inorganics, Год журнала: 2025, Номер 13(2), С. 41 - 41

Опубликована: Фев. 1, 2025

Six N^C^N cyclometalated Ni(II) complexes [Ni(N^C^N)Cl] or [Ni(N^C^N’)Br] with symmetric non-symmetric N^C^N’ ligands in which the peripheral N-groups were varied pyridine (Py), 4-thiazole (4Tz), 2-thiazole (2Tz), and 2-benzothiazole (2Btz) complementing previously reported di(2-pyridyl)phenide [Ni(Py(Ph)Py)X] X = Cl Br. The synthesized from NiBr2 N^CH^N’ protoligands through base-assisted nickelation, while received N^C(Cl)^N [Ni(COD)2] (COD 1,5-cyclooctadiene). Introduction of 4Tz on both sides shifted electrochemical gap ΔEexp Eox–Ered long wavelength UV-vis absorption maxima to higher energies, 2Tz leads a shift lower energies. When introducing only one as groups, remaining PhPy moiety dominates electronic properties electrochemistry photophysics are very similar Py(Ph)Py derivatives. In contrast this, introduction 2Btz shifts values regardless two groups character frontier molecular orbitals complexes, DFT calculations show. Long-wavelength absorptions vary 416 443 nm, their energies correlate well first reduction potentials. Negishi-type C–C cross-coupling reactions gave total yields ranging 1 60% 44%. reactivities roughly Facilitated (E around –2 higher) goes generally along improved performance, making thiazole-containing interesting candidates for such catalysis.

Язык: Английский

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Development of a Scalable Synthesis of Casdatifan (AB521), a Potent, Selective, Clinical-Stage Inhibitor of HIF-2α

Organic Process Research & Development, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

Язык: Английский

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Dearomative Alkylation of Heteroarenium Salts via Blue Light Enabled Homolytic C–C Bond Cleavage

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

Alkyl substituted nitrogen heterocycles are important building blocks in drug molecules, agrochemicals, and materials. Herein we report a simple efficient way to prepare such compounds by coupling alkyl halides with heteroarenium salts. Detailed experimental computational studies indicate that this reaction goes through radical avoids the formation of undesired homocoupling salts via recycling dimers C–C bond cleavage under blue light.

Язык: Английский

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New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Язык: Английский

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Sulfonyl hydrazides as a general redox-neutral platform for radical cross-coupling

Science, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Язык: Английский

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