Recent advances in nickel-catalyzed C–C and C–N bond formation via HA and ADC reactions

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(19), С. 4213 - 4227

Опубликована: Янв. 1, 2021

In this review article, recent advances in nickel-catalyzed hydrogen auto-transfer (HA) and acceptorless dehydrogenative coupling (ADC) reactions for the construction of C–C C–N bonds have been discussed.

Язык: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4607 - 4647

Опубликована: Янв. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Язык: Английский

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α‐Alkylation of Ketones with Secondary Alcohols Catalyzed by Well‐Defined Cp*Co^III‐Complexes

ChemSusChem, Год журнала: 2019, Номер 12(15), С. 3463 - 3467

Опубликована: Июнь 26, 2019

Although α-alkylation of ketones with primary alcohols by transition-metal catalysis is well-known, the same process secondary arduous and complicated self-condensation. Herein a well-defined, high-valence cobalt(III)-catalyst was applied for successful alcohols. A wide-variety alcohols, which include cyclic, acyclic, symmetrical, unsymmetrical compounds, employed as alkylating agents to produce β-alkyl aryl ketones.

Язык: Английский

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Sustainable and Selective Alkylation of Deactivated Secondary Alcohols to Ketones by Non‐bifunctional Pincer N‐heterocyclic Carbene Manganese

ChemSusChem, Год журнала: 2020, Номер 13(10), С. 2557 - 2563

Опубликована: Март 31, 2020

Abstract A sustainable and green route to access diverse functionalized ketones via dehydrogenative–dehydrative cross‐coupling of primary secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N‐heterocyclic carbene Mn complex displays high activity selectivity. variety are well tolerant result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds direct outer‐sphere mechanism the dehydrogenation alcohol substrates plays vital role rate‐limiting step.

Язык: Английский

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Diastereo- and Enantioselective Construction of Spirocycles by Nickel-Catalyzed Cascade Borrowing Hydrogen Cyclization

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(1), С. 53 - 59

Опубликована: Дек. 24, 2020

Spirocycles play an important role in drug discovery and development owing to their inherent three-dimensionality structural novelty. Despite the recent significant progress, straightforward catalytic asymmetric assembly of spirocyclic scaffolds with multiple stereocenters from readily available starting materials remains a formidable challenge. Herein, we develop unprecedented nickel-catalyzed one-pot synthesis enantioenriched spiroindanones easily 1,6-enynes o-formylarylboronic acids. The reaction proceeds smoothly under redox-neutral conditions, without need for additional hydrogen donor, features broad substrate scope excellent regio-, enantio-, diastereoselectivity.

Язык: Английский

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Nickel-Catalyzed Guerbet Type Reaction: C-Alkylation of Secondary Alcohols via Double (de)Hydrogenation

Organic Letters, Год журнала: 2021, Номер 23(9), С. 3320 - 3325

Опубликована: Апрель 21, 2021

Acceptorless double dehydrogenative cross-coupling of secondary and primary alcohols under nickel catalysis is reported. This Guerbet type reaction provides an atom- a step-economical method for the C-alkylation mild, benign conditions. A broad range substrates including aromatic, cyclic, acyclic, aliphatic was well tolerated. Interestingly, cholesterol derivatives cyclopentanol with various were also demonstrated.

Язык: Английский

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Guerbet-type β-alkylation of secondary alcohols catalyzed by chromium chloride and its corresponding NNN pincer complex

Catalysis Science & Technology, Год журнала: 2022, Номер 12(15), С. 4753 - 4762

Опубликована: Янв. 1, 2022

β-Alkylation of alcohols has been efficiently accomplished using readily available 3d metal Cr under microwave conditions in air. Well-defined molecular is involved with a KIE 7.33 and insertion α-alkylated ketone into Cr–H bond as the RDS.

Язык: Английский

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Zn(II)‐Stabilized Azo‐Anion Radical Catalyzed Sustainable C−C Bond Formation: Regioselective Alkylation of Fluorene, Oxindole, and Indoles

ChemCatChem, Год журнала: 2024, Номер 16(10)

Опубликована: Фев. 7, 2024

Abstract Herein we report a sustainable approach for the alkylation of ketones, 9 H ‐fluorene, oxindole, and indole using alcohols as alkylating agent catalyzed by well‐defined air‐stable zinc catalyst ( 1 ) tridentate redox non‐innocent arylazo ligand, 2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline L ). 2–3 mol % efficiently produces substituted α‐alkylated 9‐alkylated fluorenes, C3 ‐alkylated oxindoles, indoles in moderate to good isolated yields. In aerial condition, formation bis(indolyl)methane (BIMs) derivatives were observed when subjected primary alcohols. A few drug molecules containing BIMs prepared The exhibited chemoselectivity during functionalization fluorene with oleyl alcohol β‐citronellol. control experiments, including deuterium labeling performed unveil reaction mechanism indicate that one‐electron reduced azo‐anion radical species [ ]‐formed situ, acts active catalyst. All events occur at redox‐active aryl‐azo which reservoir hydrogen electrons throughout catalytic cycle, keeping Zn(II)‐center template.

Язык: Английский

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Nickel-Catalyzed Direct Alkenylation of Methyl Heteroarenes with Primary Alcohols

The Journal of Organic Chemistry, Год журнала: 2019, Номер 84(15), С. 9819 - 9825

Опубликована: Июль 2, 2019

An efficient nickel-catalyzed acceptorless dehydrogenative coupling of methyl-substituted heteroarenes with primary alcohols is achieved using an in situ generated complex inexpensive NiBr2 and readily available 8-aminoquinoline picolinic amide ligand. The protocol operationally simple scalable furnishes a series high-value 2-alkenylheteroarenes good yields (up to 88%) exclusive E-selectivity. reaction proceeds the release water molecular hydrogen, which was analyzed through gas chromatography validate mechanism.

Язык: Английский

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Iron-Catalyzed Ligand Free α-Alkylation of Methylene Ketones and β-Alkylation of Secondary Alcohols Using Primary Alcohols

The Journal of Organic Chemistry, Год журнала: 2019, Номер 84(18), С. 11676 - 11686

Опубликована: Авг. 9, 2019

Herein, we demonstrate a general and broadly applicable catalytic cross coupling of methylene ketones secondary alcohols with series primary to disubstituted branched ketones. A simple nonprecious Fe2(CO)9 catalyst enables one-pot oxidations both range gem-bis(alkyl) number bond activations formations selectively occurred in one pot provide the ketone products. Coupling reactions can be performed gram scale successfully applied synthesis an Alzehimer's drug. Alkylation steroid hormone achieved. single sequential double alkylation bis-hetero aryl using two different alcohols. Preliminary mechanistic studies IR probe, deuterium labeling, kinetic experiments established participation borrowing-hydrogen process Fe catalyst, reaction produces H2 H2O as byproducts.

Язык: Английский

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