CO2 as a C1-building block for the catalytic methylation of amines

Jacquet, Olivier; Frogneux, Xavier; Gomes, Christophe Das Neves; Cantat, Thibault

doi:10.1039/c3sc22240c

Cited by 326 publications

(192 citation statements)

References 34 publications

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“…3, equation c) 32 . In the same year, Cantat et al 33 reported zinc catalysts able to perform the methylation of amines with CO 2 and hydrosilanes at low pressure. Furthermore, the selective reduction of ureas was possible under similar reaction conditions.…”

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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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 is a waste product from all combustion processes and represents a potential and alternative carbon feed stock 1,2 for the preparation of a variety of useful chemicals including MeOH, 3,4 urea, 5 lactones, 6 various heterocycles, [7][8][9][10][11] biodegradable polymers, [12][13][14][15][16] and carboxylated structures [17][18][19][20][21] among others. [22][23][24] In particular, direct CO 2 utilisation for the preparation of polycarbonates, poly(ether)carbonates and polyurethanes is a viable technology to access novel tailor-made CO 2 -based materials. 25 The development of cost-and energy-efficient synthetic methodologies to exploit CO 2 as a C 1 synthon could eventually loosen the grip on our fossil fuel dependence, contributing to a reduction of the overall CO 2 emissions and offering tangible alternatives to physical sequestration methods.…”

Section: Introductionmentioning

confidence: 99%

Sustainable conversion of carbon dioxide: the advent of organocatalysis

2015

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The conversion of carbon dioxide (CO 2 ), an abundant renewable carbon reagent, into chemicals of academic and industrial interest is of imminent importance to create a higher degree of sustainability in chemical processing and production. Recent progress in this field is characterised by a plethora of organic molecules able to mediate the conversion of suitable substrates in the presence of CO 2 into a variety of value-added commodities with advantageous features combining cost-effectiveness, metalfree transformations and general substrate activation profiles. In this review, the latest developments are discussed in the field of CO 2 catalysis with a focus on organo-mediated conversions and their increasing importance as to serve as practicable alternatives for metal-based processes. Also a critical assessment of the state-of-the-art is presented with attention on those features that need further attention to lift the usefulness of organocatalysis in the production of organic molecules of potential commercial interest.

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“…In this context, Zn(II)-NHC complexes represent a remarkable example. They have shown to be particularly active in reactions involving the fixation of CO 2 , such as the methylation of amines [3], or the synthesis of cyclic carbonates from epoxides [4]. In addition, they are employed in the synthesis of polyurethanes [5] and in the polymerization of D,L-lactide [6].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and catalytic activity of stable [(NHC)H][ZnXY2] (NHC =N-Heterocyclic carbene, X, Y = Cl, Br) species

Santoro

Nahra

Cordes

et al. 2016

Journal of Molecular Catalysis A: Chemical

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Graphical Abstract Highlights• A library of stable [(NHC)H][ZnXY 2 ] species was synthesized• The structure of the salts was unambiguously assessed by X-ray diffraction analyses• The catalytic activity of the novel species was tested in the methylation of amines with CO 2 as carbon feedstock AbstractThe synthesis and characterization of imidazol(in)ium-based zinc(II) halide salts are reported.These compounds present interesting structural features and exhibit high stability. Their catalytic activity was explored in the methylation of amines with CO 2 and PhSiH 3 .

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CO2 as a C1-building block for the catalytic methylation of amines

Cited by 326 publications

References 34 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Sustainable conversion of carbon dioxide: the advent of organocatalysis

Synthesis, characterization and catalytic activity of stable [(NHC)H][ZnXY2] (NHC =N-Heterocyclic carbene, X, Y = Cl, Br) species

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