Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide

Wu, Lipeng; Liu, Qiang; Fleischer, Ivana; Jackstell, Ralf; Beller, Matthias

doi:10.1038/ncomms4091

Cited by 197 publications

(92 citation statements)

References 44 publications

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“…Key to success was an unprecedented in situ formation of CO from CO 2 (Fig. 7c) 85 . In contrast to previously reported hydrocarboxylation reactions of alkenes with CO 2 , similar carboxylated products are obtained, but the presence of stoichiometric amounts of strong and expensive reductants like Et 2 Zn and silanes is avoided.…”

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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“…The supercritical CO 2 process simulation was based on the literature in which the CO 2 -based methoxycarbonylation reaction was first performed under batch conditions, 20 as well as on further study of the reaction under continuous supercritical conditions. 21 Ethylene and CO 2 gas feeds are compressed to a pressure of 120 bar.…”

Section: Methyl Propionate Synthesis In the Lucite Alpha Processmentioning

confidence: 99%

“…22 Synthesis of the methyl propionate is achieved in the first step of the process through the hydroesterification of ethylene with methanol and carbon monoxide. As it was shown by the group of Beller, 20 synthesis of methyl propionate is also possible via the novel alkoxycarbonylation reaction, simply by replacing the carbon monoxide feedstock with CO 2 and using a more robust and less expensive catalyst. An issue to be considered for practical application is that the ionic liquid phase is continually diluted with water produced in the reaction.…”

Section: Introductionmentioning

confidence: 99%

Life cycle assessment of novel supercritical methyl propionate process with carbon dioxide feedstock

et al. 2017

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“…[7, 6a] More recently, Skrydstrup and co-workers [8] developed an elegant system for ex situ generation of CO in a sealed twochamber system (COware) by using 9-methylfluorene-9-carbonyl chloride (COgen) as a solid CO precursor (Scheme 1). By using this system they reported several efficient palladium-catalyzed carbonylation reactions, and they also used this technique for selective 13 C-isotope labeling. As an example, they demonstrated the reductive carbonylation of aryl iodides with COgen and potassium formate as a hydride source.…”

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Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

et al. 2014

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Carbonylation reactions represent useful tools for organic synthesis. However, the necessity to use gaseous carbon monoxide is a disadvantage for most organic chemists. To solve this problem, novel protocols have been developed for conducting palladium-catalyzed reductive carbonylations of aryl bromides and alkoxycarbonylations using paraformaldehyde as an external CO source (CO gas free). Hence, aromatic aldehydes and esters were synthesized in moderate to good yields.

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Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide

Cited by 197 publications

References 44 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Life cycle assessment of novel supercritical methyl propionate process with carbon dioxide feedstock

Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

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