Liberation of methyl acrylate from metallalactone complexes via M–O ring opening (M = Ni, Pd) with methylation agents

Lee, S. Y. Tina; Ghani, Amylia A.; D’Elia, Valerio; Cokoja, Mirza; Herrmann, Wolfgang A.; Basset, Jean‐Marie; Kühn, Fritz E.

doi:10.1039/c3nj00693j

Cited by 43 publications

(30 citation statements)

References 55 publications

(11 reference statements)

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“…Scheme 24. Nickelalactone ring opening triggered by methyl electrophiles [90,91] Limbach and Hofmann reported a comprehensive theoretical study on the mechanism of the nickelmediated synthesis of methyl acrylate from ethylene, CO 2 and methyl iodide [92]. DFT calculations revealed an SN 2 -type mechanism for the alkylation of the carboxylate ligand, which explain the experimental observations gathered by the groups of Rieger and Kühn.…”

Section: Scheme 23supporting

confidence: 52%

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Juliá‐Hernández¹,

Gaydou²,

Serrano³

et al. 2016

Topics in Current Chemistry Collections

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Abstract. The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO 2 ) as a C1 building block has recently attracted a considerable attention. Among the different alternatives in CO 2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via wasteproducing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO 2 by using cheap and available Ni or Fe catalytic species.

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Section: Scheme 23supporting

confidence: 52%

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Juliá‐Hernández¹,

Gaydou²,

Serrano³

et al. 2016

Topics in Current Chemistry Collections

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“…Importantly, DFT calculations revealed that the rate-determining step corresponded to the addition of methyl iodide. In line with this notion, the authors found that the inclusion of methyl triflate (MeOTf) significantly enhanced the rate of the reaction [91]. Unlike the use of methyl iodide, the reaction of MeOTf turned out to be particularly efficient with dppe, dppp, or even dppb, whereas the employment of TMEDA failed to provide the targeted methyl acrylate.…”

Section: Carboxylation Of Ethylene With Co 2 En Route To Acrylate Dermentioning

confidence: 82%

“…Scheme 24 Nickelalactone ring opening triggered by methyl electrophiles [90,91] (c-nickelalactone), in which the Lewis acid is coordinated to the carboxylate fragment, ultimately leading to a four-membered nickelacycle via b-hydride elimination and subsequent migratory insertion (Scheme 25). The latter species underwent formation of acrylate Ni(0) p-complexes upon addition of a base such as BTPP [tert-butyliminotri(pyrrolidino)phosphorane] or DBU.…”

Section: = I Otfmentioning

confidence: 99%

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

et al. 2016

View full text Add to dashboard Cite

The sustainable utilization of available feedstock materials for preparing valuable compounds holds great promise to revolutionize approaches in organic synthesis. In this regard, the implementation of abundant and inexpensive carbon dioxide (CO2) as a C1 building block has recently attracted considerable attention. Among the different alternatives in CO2 fixation, the preparation of carboxylic acids, relevant motifs in pharmaceuticals and agrochemicals, is particularly appealing, thus providing a rapid and unconventional entry to building blocks that are typically prepared via waste-producing protocols. While significant advances have been realized, the utilization of simple unsaturated hydrocarbons as coupling partners in carboxylation events is undoubtedly of utmost academic and industrial relevance, as two available feedstock materials can be combined in a catalytic fashion. This review article aims to describe the main achievements on the direct carboxylation of unsaturated hydrocarbons with CO2 by using cheap and available Ni or Fe catalytic species.

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“…However, later considerations revealed that the release of acrylic acid is also thermodynamically unfavored [54,55]. As a result, the cleavage of nickelalactones by various electrophiles such as alkyl halides (see, e.g., [56][57][58]), protons (see, e.g., [59,60]), and Lewis acids (see, e.g., [60,61]) has been studied, but a catalytic process could not be established until a recent report by Limbach and co-workers [62].…”

Section: Nickel-catalyzed Reactionsmentioning

confidence: 99%

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

Brill

Lazreg

Cazin

et al. 2015

Topics in Organometallic Chemistry

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The development of sustainable chemical processes is a long-standing challenge. Carbon dioxide represents a renewable C1 building block for organic synthesis and industrial applications as an alternative to other common feedstocks which are based on natural gas, petroleum oil, or coal. Apart from the advantages associated with the nontoxicity and abundance of CO 2 , its utilization further enables the reduction in its atmospheric content, which contributes significantly to the greenhouse effect. Although widespread application of CO 2 in organic synthesis -even on an industrial scale -will not be able to fully compensate for the steadily increasing atmospheric quantities produced (mainly by the combustion of fuels), ecological and economical factors make its usage highly desirable. Therefore, tremendous efforts toward activation and utilization of CO 2 have been made by the scientific community over the last 30 years, and, as a result, the number of highly efficient transition metal-catalyzed CO 2 -incorporative reactions has increased dramatically, especially within the last decade. The achievements in the development of sustainable and economic chemical processes for the carboxylation of organic molecules with CO 2 are presented in detail in this chapter.

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Liberation of methyl acrylate from metallalactone complexes via M–O ring opening (M = Ni, Pd) with methylation agents

Cited by 43 publications

References 55 publications

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Ni- and Fe-catalyzed Carboxylation of Unsaturated Hydrocarbons with CO2

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

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