α‐Methylation of Ketones with Methanol Catalyzed by Ni/SiO2‐Al2O3

Charvieux, Aubin; Duguet, Nicolas; Métay, Estelle

doi:10.1002/ejoc.201900602

Cited by 21 publications

(12 citation statements)

References 39 publications

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“…To this date, no non‐noble metal based heterogeneous catalyst has been reported for this reaction. Our group has been investigating the efficiency of Ni/SiO 2 –Al 2 O 3 for the α‐alkylation of ketones with alcohols, including methanol , . Furthermore, this catalyst has been fully characterized (see ESI).…”

Section: Base Screening For the N‐alkylation Of Phenylacetamide 1a Wimentioning

confidence: 99%

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Solvent‐Free N‐Alkylation of Amides with Alcohols Catalyzed by Nickel on Silica–Alumina

et al. 2019

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The N‐alkylation of phenylacetamide with benzyl alcohol has been studied using Ni/SiO2–Al2O3. In the optimized conditions, the desired product was isolated in an excellent 98 % yield. The reaction could advantageously be performed in neat conditions, with a slight excess of amide and a catalytic amount of base. These conditions were tested on a large range of amides and alcohols, affording 24 compounds in 13 to 99 % isolated yields.

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Section: Base Screening For the N‐alkylation Of Phenylacetamide 1a Wimentioning

confidence: 99%

“…Our group has been investigating the efficiency of Ni/SiO 2 -Al 2 O 3 for the αalkylation of ketones with alcohols, including methanol. [33,34] Furthermore, this catalyst has been fully characterized (see ESI). Herein, we report our new findings on the catalytic activity of Ni/SiO 2 -Al 2 O 3 for the solvent-free N-alkylation of amides with alcohols.…”

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confidence: 99%

Solvent‐Free N‐Alkylation of Amides with Alcohols Catalyzed by Nickel on Silica–Alumina

et al. 2019

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“…Not surprisingly, heterogeneous Ni‐catalysts were also reported for the C‐methylation of ketones and indoles [50] . As an example, Métay and co‐workers demonstrated the preparation and applicability of Ni/SiO 2 −Al 2 O 3 catalyst for α ‐methylation of ketones with methanol [50] . As expected, compared to homogeneous catalysts, this Ni‐nanocatalyst needs a higher temperature (185 °C).…”

Section: Heterogeneous Catalysts For C‐methylation With Methanolmentioning

confidence: 85%

“…Next, Raney Ni‐ and other Ni‐based heterogeneous catalysts were widely applied for hydrogenations, dehydrogenations, and other reactions [49] . Not surprisingly, heterogeneous Ni‐catalysts were also reported for the C‐methylation of ketones and indoles [50] . As an example, Métay and co‐workers demonstrated the preparation and applicability of Ni/SiO 2 −Al 2 O 3 catalyst for α ‐methylation of ketones with methanol [50] .…”

Section: Heterogeneous Catalysts For C‐methylation With Methanolmentioning

confidence: 99%

Base Metal‐Catalyzed C‐Methylation Reactions Using Methanol

et al. 2021

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C‐methylation is a vitally important reaction applicable in chemical synthesis and structure‐based drug design. Notably, the “magic methyl” effect has become decisive in medicinal chemistry and drug discovery for the modulation of bio‐active properties in life science molecules. In this regard, C‐methylation reaction is widely applied chemical modification in various biomolecules, pharmaceuticals, and natural products. In general, this reaction often relies on activated, hazardous and uneconomical methyl sources such as diazomethane, dimethyl sulfate, and methyl halides. To achieve methylation reactions in a sustainable and cost‐effective manner, the use of ‘ideal’ C1 source is crucial. In this regard, methanol constitutes an expedient −CH3 source because this simple alcohol is less‐hazardous, inexpensive, and abundantly available platform chemical as well as it produces only water as the by‐product in methylation processes. Regarding potential catalysts to perform C‐methylation using methanol by hydrogen borrowing methodology, non‐noble metal‐based catalysts are highly preferable due to their unique advantages such as more abundance, inexpensive and low‐toxicity. In recent years, chemists made significant contributions towards catalytic valorization of methanol as C1 source to insert methyl groups via C−H activation in a variety of compounds and life science molecules. Consequently, in this minireview we summarize the C‐methylation process using methanol by applying Fe‐, Mn‐, Co‐ and Ni‐based catalysts as well as metal free catalysts.

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“…Electron-donating groups at the ortho-and para-positions of propiophenone derivatives provided excellent isolated yields of the corresponding methylated products (2-4). 4-Chloro-and 4-fluoro propiophenones (34,35) were dehalogenated and produced methoxy-substituted corresponding products (Scheme S1). Methyl 2-phenylacetate (36) was hydrolyzed under the reaction conditions, and the carboxylate salt of the substrate was detected.…”

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confidence: 99%