Silver Supported Nanoparticles on [Mg4Al‐LDH] as an Efficient Catalyst for the α‐Alkylation of Nitriles, Oxindoles and Other Carboxylic Acid Derivatives with Alcohols DOI Creative Commons
Luis Izquierdo‐Aranda, Rosa Adam, Jose R. Cabrero‐Antonino

et al.

ChemSusChem, Journal Year: 2023, Volume and Issue: 16(23)

Published: July 24, 2023

An efficient heterogeneous silver-catalyzed α-alkylation of nitriles and oxindoles using alcohols via borrowing hydrogen strategy has been developed for the first time. The active nanostructured material, namely [Ag/Mg4 Al-LDH], composed by silver nanoparticles (3-4 nm average particle size) homogeneously stabilized onto a [Mg4 Al-LDH] support with suitable Brønsted basic properties, constitutes stable catalyst sustainable building novel C-C bonds from C-nucleophiles. By applying this catalyst, broad range α-functionalized accessed good to excellent isolated yields without addition external bases. Moreover, nanocatalyst also demonstrated its successful application cyclization N-[2-(hydroxymethyl)phenyl]-2-phenylacetamides afford 3-arylquinolin-2(1H)-ones, through one-pot dehydrogenation intramolecular α-alkylation. Control experiments, kinetic studies, characterization data variety [Ag/LDH]-type materials confirmed role in hydrogenation steps, while matrix is able catalyze condensation. Interestingly, these studies suggest as key point activity comparison other nanocatalysts, acid-base properties material.

Language: Английский

Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds DOI
Sourajit Bera, Lalit Mohan Kabadwal, Debasis Banerjee

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 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.

Language: Английский

Citations

16
Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect DOI
Ishani Borthakur,

Anirban Sau,

Sabuj Kundu

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214257 - 214257

Published: Oct. 28, 2021

Language: Английский

Citations

77
Selective Catalytic Synthesis of α-Alkylated Ketones and β-Disubstituted Ketones via Acceptorless Dehydrogenative Cross-Coupling of Alcohols DOI

Dipanjan Bhattacharyya,

Bikash Kumar Sarmah,

Sekhar Nandi

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 869 - 875

Published: Jan. 21, 2021

Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary to α-alkylated ketones and two different β-branched are reported. Notably, this transformation is environmentally benign atom efficient H2O H2 gas as the only byproducts. The protocol extended gram-scale reaction for functionalization complex vitamin E cholesterol derivatives.

Language: Английский

Citations

58
Enable biomass-derived alcohols mediated alkylation and transfer hydrogenation DOI Creative Commons
Xixi Liu, Liang Huang,

Yuandie Ma

et al.

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

Citations

12
Iron-Catalyzed α-Methylation of Ketones Using Methanol as the C1 Source under Photoirradiation DOI

Balakumar Emayavaramban,

Priyanka Chakraborty,

Pardeep Dahiya

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(33), P. 6219 - 6223

Published: Aug. 12, 2022

A mild, environmentally benign approach for α-methylation of ketones utilizing methanol as the C1 source under visible light has been developed. The reaction conditions were favorable a wide range with both aromatic and aliphatic backbones, allowing good-to-excellent yields respective products. tentative mechanism is postulated after preliminary mechanistic kinetic experiments.

Language: Английский

Citations

33
Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis** DOI

Abir Das,

Rajib Mandal,

Harihara Subramanian Ravi Sankar

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 14, 2023

Abstract Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion π‐coupling partner between M−C with high enantio‐induction remain elusive. Using commercially available Co(II) salt chiral‐Salox ligands, we demonstrate an unusual protocol for regio‐reversal, enantioselective phosphinamide bromoalkyne desymmetrization. The reaction proceeds ligand‐assisted enantiodetermining cyclocobaltation followed by Co−C, subsequent reductive elimination, halogen exchange carboxylate resulted in P‐stereogenic compounds excellent ee (up to >99 %). isolation cobaltacycle involved catalytic cycle outcome control experiments provide support plausible mechanism.

Language: Английский

Citations

16
Ruthenium Complexes with NNN-Pincer Ligands for N-Methylation of Amines Using Methanol DOI

Mengxuan Bai,

Shengxin Zhang,

Zhengguo Lin

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(25), P. 11821 - 11831

Published: June 7, 2024

A series of ruthenium complexes (Ru1–Ru4) bearing new NNN-pincer ligands were synthesized in 58–78% yields. All the are air and moisture stable characterized by IR, NMR, high-resolution mass spectra (HRMS). In addition, structures Ru1–Ru3 confirmed X-ray crystallographic analysis. These Ru(II) exhibited high catalytic efficiency broad functional group tolerance N-methylation reaction amines using CH3OH as both C1 source solvent. Experimental results indicated that electronic effect substituents on considerably affects reactivity which Ru3 an electron-donating OMe showed highest activity. Deuterium labeling control experiments suggested dehydrogenation methanol to generate hydride species was rate-determining step reaction. Furthermore, this protocol also provided a ready approach versatile trideuterated N-methylamines under mild conditions CD3OD deuterated methylating agent.

Language: Английский

Citations

5
Well‐defined Cp*Co(III)‐catalyzed Hydrogenation of Carbonates and Polycarbonates DOI

Pardeep Dahiya,

Manoj Kumar Gangwar, Basker Sundararaju

et al.

ChemCatChem, Journal Year: 2020, Volume and Issue: 13(3), P. 934 - 939

Published: Nov. 19, 2020

Abstract We herein report the catalytic hydrogenation of carbonates and polycarbonates into their corresponding diols/alcohols using well‐defined, air‐stable, high‐valent cobalt complexes. Several novel Cp*Co(III) complexes bearing N , O ‐chelation were isolated for first time structurally characterized by various spectroscopic techniques including single crystal X‐ray crystallography. These Co(III) have shown excellent activity to produce value added from carbonate through molecular hydrogen as sole reductant or i PrOH transfer source. To demonstrate developed methodology's practical applicability, we recycled bisphenol A monomer compact disc (CD) under established reaction conditions phosphine‐free, earth‐abundant, air‐ moisture‐stable catalysts.

Language: Английский

Citations

35
Nickel‐Catalyzed Selective Synthesis of α‐Alkylated Ketones via Dehydrogenative Cross‐Coupling of Primary and Secondary Alcohols DOI

Amreen K. Bains,

Ayanangshu Biswas, Debashis Adhikari

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 364(1), P. 47 - 52

Published: Oct. 11, 2021

Abstract Herein, we describe an isolable, air‐stable, homogeneous, nickel catalyst that performs dehydrogenative cross‐coupling reaction between secondary and primary alcohols to result α‐alkylated ketone products selectively. The sequence of steps involve in this one‐pot is dehydrogenation both alcohols, condensation the aldehyde, hydrogenation situ‐generated α,β‐unsaturated ketone. Preliminary mechanistic investigation hints a radical mechanism following borrowing hydrogen reaction. magnified image

Language: Английский

Citations

28
Cobalt-Catalyzed Alkylation of Nitriles with Alcohols DOI
Arpita Singh, Michael Findlater

Organometallics, Journal Year: 2022, Volume and Issue: 41(22), P. 3145 - 3151

Published: Feb. 17, 2022

Herein, we report an operationally convenient, cobalt-catalyzed alkylation of aryl nitriles employing primary and secondary alcohols (>30 examples, up to 86% yield). The use readily available cobalt precursors the widely employed BIAN (BIAN = bis(arylimino)acenaphthene) ligand affords efficient catalytic reaction that is environmentally benign, leading formation water as only byproduct.

Language: Английский

Citations

20