Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

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Enable biomass-derived alcohols mediated alkylation and transfer hydrogenation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 15, 2024

A single-atom catalyst with generally regarded inert Zn–N4 motifs derived from ZIF-8 is unexpectedly efficient for the activation of alcohols, enabling alcohol-mediated alkylation and transfer hydrogenation. C-alkylation nitriles, ketones, N-heterocycles, amides, keto acids, esters, N-alkylation amines amides all go smoothly developed method. Taking α-alkylation nitriles alcohols as an example, starts (1) nitrogen-doped carbon support catalyzed dehydrogenation into aldehydes, which further condensed to give vinyl followed by (2) hydrogenation C=C bonds in on sites. The experimental results DFT calculations reveal that Lewis acidic Zn-N4 sites promote step activating alcohols. This first example highly catalysts various organic transformations biomass-derived alkylating reagents hydrogen donors. Using carbonyl compounds or synthesis α-alkylated appealing a sustainability perspective. Here, acting acid effectively activates thus promoting reactions using both

Language: Английский

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Recent Developments of Transition‐Metal‐Catalyzed Cross‐Coupling of Nitriles and Alcohols

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(32)

Published: Aug. 22, 2024

Abstract Cross‐coupling of nitriles and alcohols offers an environmentally friendly atom‐economical method for the synthesis various valuable compounds. These compounds include α ‐alkylated ‐olefinated nitriles, primary amines, imines, N ‐alkylation amides, ‐heterocycles, δ ‐hydroxynitriles, olefins, etc . Herein, we have reviewed recent developments (from 2013–date) transition‐metal‐catalyzed cross‐coupling alcohols. A number transition metal complexes such as noble metals Ru Ir, well base Mn, Fe, Co, Ni are presented. Moreover, different product types, reaction conditions mechanisms discussed to understand catalyst development.

Language: Английский

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

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(7)

Published: Feb. 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.

Language: Английский

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Ni₂P Nanoparticles Supported on N, P Co-Doped Carbon as Catalyst for α-Alkylation of Arylacetonitriles with Alcohols

ACS Applied Nano Materials, Journal Year: 2024, Volume and Issue: 7(8), P. 8914 - 8925

Published: April 10, 2024

The nickel phosphides have garnered increasing attention as an excellent catalytic site in the fields of electrocatalysis and hydrotreating, but their application organic synthesis remains infrequent. In this study, ammonium phosphate chloride were employed doping sources for first time to synthesize Ni-based ZIF-8 precursor via host–guest method. Subsequently, was pyrolyzed obtain Ni2P nanoparticles (NPs) supported on N, P co-doped carbon. composite materials exhibit elevated metal loading effective dispersion due synergistic combination phosphorus nickel. Specifically, compared with Ni-NC, optimal Ni2P-NCP-1 exhibits enhanced activity α-alkylation arylacetonitriles alcohols using KOH base. It shows a wide broad substrate scope at 140 °C 12 h n-octane hydrogen borrowing strategy. Through characterizations mechanistic studies, it has been discovered that introduction source not only provides more basic sites carbon matrix also leads formation NPs, which facilitates efficiency by modifying electronic structure Ni. Compared metallic Ni species, effect between acid-basic significantly influences dehydrogenation generate Ni–H species. This study successfully achieves simultaneous phosphating both support, demonstrates N2P-NCP-1 catalyst significant potential heterogeneous transformation field.

Language: Английский

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Development of an imidazole-based N,N-bidentate ligand for the manganese catalyzed direct coupling of nitriles with alcohols

RSC Advances, Journal Year: 2024, Volume and Issue: 14(19), P. 12978 - 12982

Published: Jan. 1, 2024

This work describes the manganese catalyzed direct coupling of nitriles with alcohols assistance a set simple and new imidazole-based N , -bidentate ligands.

Language: Английский

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Base metal iron catalyzed sustainable oxidation of vanillyl alcohol to vanillic acid in deep eutectic solvents and implementation of vanillic acid for fine-chemical synthesis

RSC Sustainability, Journal Year: 2023, Volume and Issue: 1(5), P. 1223 - 1232

Published: Jan. 1, 2023

In the modern era, sustainable development for production of fine chemicals from abundant biomass by utilizing various chemical transformations has become a strong trend research in scientific community.

Language: Английский

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Copper-Catalyzed C(sp³)–H Alkylation of Fluorene with Primary and Secondary Alcohols using Borrowing Hydrogen Method

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(74), P. 10144 - 10147

Published: Jan. 1, 2024

Despite the limited success of copper-catalyzed alkylations, (NNS)CuCl proved to be an effective catalyst for sp

Language: Английский

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Iron-Catalyzed sp³ C–H Alkylation of Fluorene with Primary and Secondary Alcohols: A Borrowing Hydrogen Approach

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16223 - 16241

Published: Aug. 23, 2024

The utilization of earth-abundant, cheap, and nontoxic transition metals in important catalytic transformations is essential for sustainable development, iron has gained significant attention as the most abundant metal. A mixture FeCl2 (3 mol %), phenanthroline (6 KOtBu (0.4 eqivalent) was used an effective catalyst sp3 C–H alkylation fluorene using alcohol a nonhazardous alkylating partner, eco-friendly water formed only byproduct. substrate scope includes wide range substituted fluorenes benzyl alcohols. reaction equally with challenging secondary alcohols unactivated aliphatic Selective mono-C9-alkylation yielded corresponding products good isolated yields. Various postfunctionalizations C-9 alkylated were performed to establish practical utility this alkylation. Control experiments suggested homogeneous path involving borrowing hydrogen mechanism formation subsequent reduction 9-alkylidene intermediate.

Language: Английский

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Iron and Base Catalyzed C(α)-Alkylation and One-pot Sequential Alkylation-Hydroxylation of Oxindoles with Secondary Alcohols

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(31), P. 6321 - 6330

Published: Jan. 1, 2024

Iron-catalyzed protocol was developed for the C -alkylation of 2-oxindoles with secondary alcohols as coupling partners. Alkylated were further functionalized to 3-hydroxy-3-alkyl-2-oxindoles by using air most sustainable oxidant.

Language: Английский

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