Recent advances on cross-coupling of alcohols via borrowing hydrogen catalysis

Chemical Communications, Год журнала: 2024, Номер 60(30), С. 4002 - 4014

Опубликована: Янв. 1, 2024

This article highlights the recent advances and significance of β-alkylation reactions towards synthesis higher order alcohols.

Язык: Английский

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Hydrogenation of Esters Catalyzed by Bis(N-Heterocyclic Carbene) Molybdenum Complexes

ACS Catalysis, Год журнала: 2024, Номер 14(6), С. 4082 - 4092

Опубликована: Март 1, 2024

A series of Mo complexes bearing inexpensive bidentate bis(NHC) ligands have been synthesized and characterized by NMR IR spectroscopy as well single crystal XRD analysis. These proved to be efficient for the catalytic hydrogenation aliphatic aromatic esters (>35 examples) operating at low catalyst loadings (0.5–2 mol %) temperatures (80–120 °C). Various functional groups, e.g., C═C double bonds, nitriles, alcohols, tertiary amines, halides, acetals, heteroaromatic substrates, lactones, diesters, are tolerated optimal system. Based on spectroscopic investigations, control experiments DFT computations a non-bifunctional outer-sphere mechanism is proposed.

Язык: Английский

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Amine-functionalized bifunctional Co^III-NHC complexes: highly effective phosphine-free catalysts for the α-alkylation of nitriles

Chemical Communications, Год журнала: 2024, Номер 60(23), С. 3142 - 3145

Опубликована: Янв. 1, 2024

Newly developed amine functionalized NHC-supported Co

Язык: Английский

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CrCl₂-catalyzed α-alkylation of carbonyl compounds via a borrowing hydrogen approach

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(7), С. 1955 - 1962

Опубликована: Янв. 1, 2024

A new and efficient catalytic system for sustainable α-alkylation of carbonyl compounds with alcohols via a borrowing hydrogen strategy is presented.

Язык: Английский

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Multi-hydroxyl POSS supported iridium complexes as a recyclable catalyst for selective synthesis of N-/C-substituted indoles and the total synthesis of HIV-1 fusion inhibitor

Journal of Catalysis, Год журнала: 2023, Номер 429, С. 115205 - 115205

Опубликована: Ноя. 24, 2023

Язык: Английский

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Experimental and theoretical insights for designing Zn²⁺ complexes to trigger chemo-selective hetero-coupling of alcohols

Chemical Communications, Год журнала: 2024, Номер 60(30), С. 4056 - 4059

Опубликована: Янв. 1, 2024

Designing well-defined Zn-complexes for chemo-selective cross-coupling of primary and secondary alcohols overcoming the difficulties associated with activating Zn 2+ (d 10 )-metal species.

Язык: Английский

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Ruthenium-catalyzed β-alkylation of secondary alcohols with primary alcohols: Protic N-heterocyclic carbene's promotional influence

Journal of Molecular Structure, Год журнала: 2024, Номер 1305, С. 137815 - 137815

Опубликована: Фев. 17, 2024

Язык: Английский

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Ruthenium‐Catalyzed α‐Alkylation of Arylacetonitriles with Primary Alcohols: N‐heterocyclic Carbene‐Amine's Promotional Influence

ChemistrySelect, Год журнала: 2025, Номер 10(7)

Опубликована: Фев. 1, 2025

Abstract Transition‐metal‐catalyzed α‐alkylation of nitriles with alcohols is an environmentally benign reaction, and the development simple efficient catalysts for this transformation a growing area research. In study, we report serial bidentate N ‐heterocyclic carbene (NHC) ruthenium complexes different extra donors alcohols. Through adjusting backbone NHC ligands, catalytic activities these could be controlled. The complex ( Ru3 ) bearing amine donor benzimidazolium exhibited highest activity. A large variety α‐alkylated were obtained in 30%–88% yields, by using 1 mol% amount Cs 2 CO 3 (20 mol%). Detailed control experiments deuterium‐labeling suggested that reaction proceeds via borrowing hydrogen pathway.

Язык: Английский

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Heterogeneous Mn@CeO₂ Catalyst for α-Alkylation of Ketones with Alcohols via Hydrogen-Borrowing Strategy

ACS Omega, Год журнала: 2025, Номер 10(9), С. 9649 - 9660

Опубликована: Фев. 24, 2025

Construction of a C-C bond via alkylation ketones with alcohol as the alkylating source by employing hydrogen-borrowing strategy is attracting significant attention and highly appealing due to its simplicity, cost-effectiveness, environmental benefits, fact that water only byproduct. The development heterogeneous catalysts based on nonprecious base metals progressing rapidly. Our newly disclosed manganese-doped cerium oxide nanocomposite (10 wt % Mn@CeO2) stands out cost-efficient air-stable catalyst, synthesized through straightforward coprecipitation method employed for α-alkylation primary alcohols strategy. X-ray diffraction (XRD) analysis confirms high crystallinity CeO2, while field emission scanning electron microscopy (FE-SEM) high-resolution transmission (HR-TEM) images reveal MnO2 nanoparticles, measuring 19 nm in size, uniformly decorated rod-shaped CeO2 which have size 33 nm. photoelectron spectroscopy (XPS) uncovers presence Mn4+ species embedded nanorods. Electron paramagnetic resonance (EPR) further indicates surface defects contribute impressive catalytic yield, ranges from 70 98% α-alkylated ketones. Thermogravimetric (TGA) demonstrates remarkable thermal stability maintaining up 800 °C. Additionally, inductively coupled plasma mass spectrometry (ICP-MS) no leaching Mn ions, emphasizing heterogeneity catalyst. Remarkably, 10 Mn@CeO2 recycled six cycles loss activity. This study underscores synergistic effect between metal redox pair key exceptional activity reactions, making promising catalyst sustainable efficient formation.

Язык: Английский

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Alkoxide Trap in Transition‐Metal‐Catalyzed Dehydrogenative Coupling and Borrowing Hydrogen Reactions

ChemCatChem, Год журнала: 2024, Номер 16(20)

Опубликована: Июль 2, 2024

Abstract Dehydrogenative coupling (DC) and borrowing hydrogen(ation) (BH) reactions are crucial in modern organic synthesis, offering efficient sustainable ways to create valuable compounds. However, they often face a significant challenge: the alkoxide trap. This Concept explores trap DC BH reactions, starting with basic mechanisms role of intermediates. It then examines how leads catalyst deactivation reduced selectivity, influenced by thermodynamic kinetic factors. To address this, we review recent advances design, ligand engineering, optimized reaction conditions, along use in‐situ spectroscopy computational modelling, better understand underlying processes guide rational development. Furthermore, this highlights broad applicability DC, across various substrates, underscoring urgency addressing issue unlock their full synthetic potential.

Язык: Английский

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