Recycling of Carbon and Silicon Wastes: Room Temperature Formylation of N–H Bonds Using Carbon Dioxide and Polymethylhydrosiloxane

Jacquet, Olivier; Gomes, Christophe Das Neves; Ephritikhine, Michel; Cantat, Thibault

doi:10.1021/ja211527q

Cited by 346 publications

(203 citation statements)

References 22 publications

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“…Surprisingly, the corresponding dimethylated anilines were produced with nearly complete conversion and excellent selectivity (88-92%) (see ESI † Supplementary Table S9, Products 7`a-7`h), which is similar to the reported activities of homogenous catalysts with the use of a strong acid additive. 1,3,[9][10][11][12][13][14] This unexpected conversion of anilines into N,N-dimethylanilines indicated the catalytic superiority of the heterogeneous Pd 47 Ag 53 nano-alloy.…”

Section: Resultsmentioning

confidence: 85%

“…Amine methylation leads to the formation of methylamine, 1 dimethylamine 2 and formamide, 3 which are used as platform chemicals for the synthesis of fertilizers, fungicides, synthetic leathers, and polymers and are directly used as solvents and formulation agents. 3 The most common syntheses for the methylation of amines involve the use of methyl iodide, 4,5 dimethyl sulfate, 6 formaldehyde 7 or diazomethane 8 as methylating reagents with excellent reactivity.…”

Section: Introductionmentioning

confidence: 99%

“…3 The most common syntheses for the methylation of amines involve the use of methyl iodide, 4,5 dimethyl sulfate, 6 formaldehyde 7 or diazomethane 8 as methylating reagents with excellent reactivity. However, their toxicity and the stoichiometric generation of inorganic salt wastes raise environmental concerns.…”

Section: Introductionmentioning

confidence: 99%

“…From this perspective, there have been various attempts at N-methylation by using a C 1 -building block source (CO 2 , formic acid) and/or a reductant (H 2 , silanes and boranes) with organometallic catalysts, including rhodium, ruthenium and zinc complexes. 1,3,[9][10][11][12][13][14] However, these homogenous catalysts require challenging synthesis processes with an elaborately designed ligand complex, which is difficult to separate and recycle from the products. 15 Furthermore, additives such as organic acids are needed for good performance, and high pressure and/or temperature are required.…”

Section: Introductionmentioning

confidence: 99%

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Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

2015

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The methylation of amines for the synthesis of methylamines and dimethylamines as platform chemicals has been attempted mostly by homogeneous catalysts with acid additives. However, there are scarcely any reports on heterogeneous catalytic methylation reactions except for a routine approach under high temperature and high pressure of CO 2 and H 2 gases for extended reaction times. Here we report a heterogeneously catalyzed selective methylation of aromatic amines using reactive and nontoxic formic acid as the only source for the construction of methyl groups, under ambient pressure in an additive-free one-pot reaction condition. Equal proportions of Pd and Ag in the PdAg/Fe 3 O 4 /N-rGO catalyst deliver highly selective amine methylation without aromatic ring hydrogenation, as the strained Pd in the alloy is combined with the graphene-derived support, preventing nanoparticle agglomeration and the action of magnetite as a promoter. Both N-methylation and N,N-dimethylation of various substituted aromatic amines were performed with complete conversion and excellent 90-97% selectivity by controlling the reaction times in the range of 10-24 h at 140°C without unwanted aromatic ring hydrogenation. Furthermore, the developed bimetallic catalyst provided high yields (88-91%) of methylation with CO 2 +H 2 gas under high pressure, which are as good as the results of homogenous catalysts with an acid additive. To the best of our knowledge, our use of this environmentally friendly methodology is the first time that this durable heterogeneous catalyst has readily performed highly selective methylation at ambient pressure, which is attractive for industrial applications.

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Section: Resultsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

2015

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“…Shortly afterwards, a highly active N-heterocyclic carbene organocatalyst was designed by the same group for the formylation of N-H bonds in various amines and heterocycles under very mild conditions using CO 2 and polymethylhydrosiloxane (PMHS; Fig. 3, equation b) 31 .…”

Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon-trapped in a waste product-and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO 2 and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.A more sensible resource management is the prerequisite for the sustainable development of future generations. However, when dealing with the feedstock of the chemical industry, the level of sustainability is still far from satisfactory. Until now, the vast majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass, CO 2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the amount of CO 2 has steadily increased and nowadays CO 2 is a component of greenhouse gases, which are primarily responsible for the rise in atmospheric temperature and probably abnormal changes in the global climate. This increase in CO 2 concentration is largely due to the combustion of fossil fuels, which are required to meet the world's energy demand 1 . Obviously, there is an urgent need to control CO 2 emissions and develop efficient carbon capture systems. Although the extensive use of carbon dioxide for chemical production cannot solve this problem alone, CO 2 is a useful one-carbon (C1) building block in organic synthesis due to its abundance, availability, nontoxicity and recyclability. As a result, valorization of CO 2 is currently receiving considerable and ever increasing attention by the scientific community 2-4 . However, activation and utilization of CO 2 is still problematic due to the fact that it is the most oxidized form of carbon, which is also thermodynamically stable and/or kinetically inert in certain desired transformations. Consequently, most of the known studies used highly reactive substrates and/or severe reaction conditions to activate CO 2 , limiting the application of such methods. In particular, the catalytic coupling of CO 2 with energy-rich substrates, such as epoxides and aziridines, to generate polycarbonates/polycarbamates and/or cyclic carbonates/carbamates has drawn significant attention over the past decades. To create C-C bonds with CO 2 , the use of carbon nucleophiles is specifically limited to strong nucleophilic organolithiums and Grignard reagents, as well as phenolates.

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Polymethylhydrosiloxane

Lavis

Maleczka

Chandrasekaran

et al. 2016

Encyclopedia of Reagents for Organic Synthesis

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Recycling of Carbon and Silicon Wastes: Room Temperature Formylation of N–H Bonds Using Carbon Dioxide and Polymethylhydrosiloxane

Abstract: A highly active organocatalytic system based on N-heterocyclic carbenes has been designed for the formylation of N-H bonds in a large variety of nitrogen molecules and heterocycles, using two chemical wastes: CO(2) and polymethylhydrosiloxane (PMHS).

Cited by 346 publications

References 22 publications

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

Using carbon dioxide as a building block in organic synthesis

Polymethylhydrosiloxane

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