Carbon monoxide and hydrogen (syngas) as a C1-building block for selective catalytic methylation

Kaithal, Akash; Hölscher, Markus; Leitner, Walter

doi:10.1039/d0sc05404f

Cited by 29 publications

(21 citation statements)

References 64 publications

(78 reference statements)

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“…In line with the catalytic activity of Mn-MACHO complexes for CO hydrogenation, [12,16] 3 shows a high tolerance towards the presence of CO (Table 2, Entry 7). Even with additional 5 bar of CO, a high yield of methanol was obtained.…”

supporting

confidence: 54%

Hydrogenation of CO₂ to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

2021

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Dedicated to Professor Christian Bruneau on the occasion of his 70 th birthday.The hydrogenation of CO 2 to methanol was achieved using a catalytic system comprising metal complexes of the form [Mn(CO) 2 [N(C 2 H 4 PR 2 )] (R = i Pr/Ph, [HN(C 2 H 4 PPh 2 ) 2 ] = MACHOÀ Ph) together with Lewis acid additives. Mechanistic studies suggest initial CO 2 insertion into a MnÀ H bond leads to a formate complex as resting state. By systematically balancing the interaction between the acidic additive and the catalyst, the formate ligand could be removed through esterification to [a

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confidence: 54%

Hydrogenation of CO₂ to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

2021

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“…Our group recently demonstrated that the formate ester pathway opens a possible entry into a CO hydrogenation manifold for catalytic methylation reactions using Syngas as a C1 source. 37 …”

Section: Resultsmentioning

confidence: 99%

“…Previously, the groups of Marchionna, Ohyama, , and Mahajan , investigated the catalyst system Ni(CO) 4 /base for the hydrogenation of CO in the presence of methanol, demonstrating that the resulting Ni species were operating as homogeneous catalysts. Our group recently demonstrated that the formate ester pathway opens a possible entry into a CO hydrogenation manifold for catalytic methylation reactions using Syngas as a C1 source …”

Section: Resultsmentioning

confidence: 99%

Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts

Kaithal

Werlé

Leitner

2021

JACS Au

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Alcohol-assisted hydrogenation of carbon monoxide (CO) to methanol was achieved using homogeneous molecular complexes. The molecular manganese complex [Mn(CO) 2 Br[HN(C 2 H 4 P i Pr 2 ) 2 ]] ([HN(C 2 H 4 P i Pr 2 ) 2 ] = MACHO- i Pr) revealed the best performance, reaching up to turnover number = 4023 and turnover frequency 857 h –1 in EtOH/toluene as solvent under optimized conditions ( T = 150 °C, p (CO/H 2 ) = 5/50 bar, t = 8–12 h). Control experiments affirmed that the reaction proceeds via formate ester as the intermediate, whereby a catalytic amount of base was found to be sufficient to mediate its formation from CO and the alcohol in situ . Selectivity for methanol formation reached >99% with no accumulation of the formate ester. The reaction was demonstrated to work with methanol as the alcohol component, resulting in a reactive system that allows catalytic “breeding” of methanol without any coreagents.

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“…Hence, the direct use of syngas as a C1‐building block for C‐methylation reactions is also interesting. In this regard, recently, Leitner and co‐workers [26] reported the application of syngas (CO+H 2 ) for β ‐methylation of alcohols in the presence of [Mn( i Pr‐MACHO)(CO) 2 Br] complex Mn‐catalyst ( 2 ). Under the optimized reaction conditions (2 mol% Mn‐catalyst ( 2 ), 2 equiv.…”

Section: Manganese‐catalyzed C‐methylation Reactions Using Methanolmentioning

confidence: 99%

“…The presence of the alcohol substrate is essential to facilitate the hydrogenation of carbon monoxide via formate ester as intermediate(Scheme 17). [26] …”

Section: Manganese‐catalyzed C‐methylation Reactions Using 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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Carbon monoxide and hydrogen (syngas) as a C1-building block for selective catalytic methylation

Abstract: A broadly applicable catalytic process for the selective β-methylation of alcohols is presented using syngas (CO/H2) directly as a C1 building block and the shown manganese complex in the presence of a base as the catalytic system.

Cited by 29 publications

References 64 publications

Hydrogenation of CO₂ to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

Hydrogenation of CO₂ to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts

Base Metal‐Catalyzed C‐Methylation Reactions Using Methanol

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Carbon monoxide and hydrogen (syngas) as a C1-building block for selective catalytic methylation

Abstract: A broadly applicable catalytic process for the selective β-methylation of alcohols is presented using syngas (CO/H2) directly as a C1 building block and the shown manganese complex in the presence of a base as the catalytic system.

Cited by 29 publications

References 64 publications

Hydrogenation of CO2 to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

Hydrogenation of CO2 to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts

Base Metal‐Catalyzed C‐Methylation Reactions Using Methanol

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Hydrogenation of CO₂ to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

Hydrogenation of CO₂ to Methanol with Mn‐PNP‐Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed