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

Juliá‐Hernández, Francisco; Gaydou, Morgane; Serrano, Eloisa; Gemmeren, Manuel van; Martı́n, Rubén

doi:10.1007/978-3-319-49784-6_4

Cited by 4 publications

(3 citation statements)

References 97 publications

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“…Therefore, novel and efficient catalytic processes for CO 2 functionalization are highly valuable. Two major approaches for the functionalization of CO 2 , i.e., "horizontal" and "diagonal" (reductive) approaches, evolved, and they both require the use of high-energy co-reactants, catalysts, and often stringent reaction conditions to overcome the kinetic barrier (Scheme 13) [96][97][98][99][100][101][102][103][104][105].…”

Section: Functionalization Of Carbon Dioxidementioning

confidence: 99%

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Molecular Catalysis for Utilizing CO2 in Fuel Electro-Generation and in Chemical Feedstock

Leung¹,

Ho²

2019

Catalysts

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Processes for the conversion of CO2 to valuable chemicals are highly desired as a result of the increasing CO2 levels in the atmosphere and the subsequent elevating global temperature. However, CO2 is thermodynamically and kinetically inert to transformation and, therefore, many efforts were made in the last few decades. Reformation/hydrogenation of CO2 is widely used as a means to access valuable products such as acetic acids, CH4, CH3OH, and CO. The electrochemical reduction of CO2 using hetero- and homogeneous catalysts recently attracted much attention. In particular, molecular CO2 reduction catalysts were widely studied using transition-metal complexes modified with various ligands to understand the relationship between various catalytic properties and the coordination spheres above the metal centers. Concurrently, the coupling of CO2 with various electrophiles under homogeneous conditions is also considered an important approach for recycling CO2 as a renewable C-1 substrate in the chemical industry. This review summarizes some recent advances in the conversion of CO2 into valuable chemicals with particular focus on the metal-catalyzed reductive conversion and functionalization of CO2.

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Section: Functionalization Of Carbon Dioxidementioning

confidence: 99%

“…Schematic illustration of thermodynamic barrier for CO 2 functionalization[96][97][98][99][100][101][102][103][104][105].…”

mentioning

confidence: 99%

Molecular Catalysis for Utilizing CO2 in Fuel Electro-Generation and in Chemical Feedstock

Leung¹,

Ho²

2019

Catalysts

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“…work in the late 1970s, impressive progress has been made toward establishing an effective CO 2 -to-acrylate process. 16,17 This review covers research on the direct functionalization of alkenes (ethylene in particular) with the use of CO 2 as the carboxylation reagent. General principles and key steps of this transformation are discussed in the context of the different transition-metal catalysts used.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Acrylic Acid Derivatives from CO2 and Ethylene

Wang

Sun

2017

Chem

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The synthesis of acrylic acid and its derivatives with the use of CO 2 and ethylene feedstock is an exciting yet extremely challenging reaction. In addition to the inherent stability of CO 2 , other challenges arise, such as the elimination of b-hydride from metallalactone to release free acrylate. Since the groundbreaking work more than three decades ago, tremendous efforts have been made to realize an effective catalytic system. From historical findings to recent progress, this review gives a comprehensive overview of this reaction. Reactions mediated by different transition-metal complexes and mechanistic details are discussed in depth.

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Mechanistic Insights into the Nickel-Catalyzed Regioselective Carboxylation of Allylic Alcohols

Liu

et al. 2021

Organometallics

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The recently reported nickel-catalyzed direct carboxylation of allylic alcohol eliminates the necessity for preactivation of substrates in traditional strategies and generates linear β, γ-unsaturated carboxylic acids with high E/Z selectivity. Motivated by the significant experimental advantages and the mechanistic ambiguity (in the C−O activation mode of the allylic alcohol, the rate-and regio-/stereoselectivity-determining steps, etc.), we conducted a detailed study on the mechanism of Nicatalyzed carboxylation of allylic alcohols with density functional theory calculations. It is found that the reaction occurs via the activation of allylic alcohol, oxidative ligation, reduction, and carboxylation steps. The rate-determining step is the first step, in which the moisture of the reaction system plays a critical role. Through the hydrogen bonding network formed between water and the substrate, "proton-relay" occurs easily to generate the allylic hydrogen carbonate and to undergo the subsequent oxidative ligation steps. Meanwhile, the steric hindrance between CO 2 and the allylic group during the coordination of CO 2 is mainly responsible for the regioselectivity on the terminal carbon atom, and the E/Z selectivity is mainly determined by the thermodynamic stability of the E-substrates.

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

Cited by 4 publications

References 97 publications

Molecular Catalysis for Utilizing CO2 in Fuel Electro-Generation and in Chemical Feedstock

Molecular Catalysis for Utilizing CO2 in Fuel Electro-Generation and in Chemical Feedstock

Synthesis of Acrylic Acid Derivatives from CO2 and Ethylene

Mechanistic Insights into the Nickel-Catalyzed Regioselective Carboxylation of Allylic Alcohols

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