Electrocarboxylation of chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline

Fabre, Paul-Louis; Reynes, Olivier

doi:10.1016/j.elecom.2010.07.020

Cited by 17 publications

(20 citation statements)

References 28 publications

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“…Derivatives of cyanoacetic acid are precious starting materials in pharmaceutical and agrochemical synthesis [137]. When the anodic reaction is the oxidation of a halide, lower current efficiencies can be attributed to a successive oxidation and reduction of respectively halides and halonium species.…”

Section: Reviewmentioning

confidence: 99%

“…Redox mediators allow working at a less negative cathodic potential, which results in a better energy efficiency and a more selective CO 2 fixation [ 128 ]. The most common redox mediators are organometallic nickel [ 129 – 131 ], palladium [ 132 ] and cobalt complexes [ 133 – 137 ].…”

Section: Reviewmentioning

confidence: 99%

“…A significant effort has been devoted to efficiently produce cyanoacetic acid through CO 2 fixation in chloroacetonitrile, as an alternative for the hazardous synthesis via alkali metal cyanides [ 137 , 145 – 146 ]. Derivatives of cyanoacetic acid are precious starting materials in pharmaceutical and agrochemical synthesis [ 137 ]. When the anodic reaction is the oxidation of a halide, lower current efficiencies can be attributed to a successive oxidation and reduction of respectively halides and halonium species.…”

Section: Reviewmentioning

confidence: 99%

See 2 more Smart Citations

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Matthessen¹,

Fransaer²,

Binnemans

et al. 2014

Beilstein J. Org. Chem.

171

130

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SummaryThe near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process.

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Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

See 1 more Smart Citation

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Matthessen¹,

Fransaer²,

Binnemans

et al. 2014

Beilstein J. Org. Chem.

171

130

View full text Add to dashboard Cite

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“…Meanwhile, studies have indicated that silver (Ag) exhibits extraordinary electrocatalytic activities toward the reduction of organic halides [13,[18][19][20][21][22][23]43,44]. Although many studies have investigated electroreduction and electrocarboxylation of organic chlorides, most of them focused on monochloride compounds [19,21,22,[40][41][42][43][44]. Only a few studies have examined the electroreduction of polyhalidecompounds [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59], such as dichloromethane, trichloromethane, tetrachloromethane, and hexachlorocyclohexane.…”

Section: Introductionmentioning

confidence: 99%

“…Electrocarboxylation of organic halides is a potential facile means to synthesize carboxylated products. Homogeneous [40][41][42] and heterogeneous [19,21,22,43,44] catalytic methods have been adopted to optimize this reaction because of the negative reduction potential of organic chlorides. A good catalytic electrode material can effectively reduce the reduction potential and improve the reaction.…”

Section: Introductionmentioning

confidence: 99%

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

et al. 2017

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Carbon dioxide (CO 2 ) is the largest contributor to the greenhouse effect, and fixing and using this greenhouse gas in a facile manner is crucial. This work investigates the electrocarboxylation of dichlorobenzenes with the atmospheric pressure of CO 2 in an undivided cell with an Ag cathode and an Mg sacrificial anode. The corresponding carboxylic acids and their derivatives, which are important industrial and fine chemicals, are obtained. To deeply understand this reaction, we investigate the influence of various reaction conditions, such as supporting electrolyte, current density, electric charge, and reaction temperature, on the electrocarboxylation yield by using 1,4-dichlorobenzene as the model compound. The electrochemical behavior of dichlorobenzenes is studied through cyclic voltammetry. The relation among the distinct electronic effects of dichlorobenzenes, the electrochemical characteristics of their reduction, and the distribution law of target products is also established.

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Electrochemistry of Organocobalt Compounds

Buriez

Labbé

2022

Patai's Chemistry of Functional Groups

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This chapter deals with the electrochemical preparation and reactivity of electrogenerated alkyl‐ and aryl‐cobalt complexes. Alkylcobalts have originally been obtained from the electrochemical reduction of square planar cobalt(II) complexes, mimicking the ability of vitamin B12 to reversibly form cobalt–carbon bonds. In this respect, the electrosynthetic processes involving alkyl halides and Schiff‐base or porphyrin cobalt complexes have been extensively developed on various substrates, allowing reductive dehalogenation of the alkyl halides, their cyclization, carboxylation, etc. The reduction waves of both the cobalt(II) precursors and the alkylcobalt(III) complexes that result from the reaction of electrogenerated cobalt(I) on alkyl halides are observed in the [−1 V vs. SCE/−1.4 V vs. SCE] region, making accurate mechanistic predictions difficult from simple electrolyses. However, thorough electroanalytical investigations have provided robust reaction frameworks, namely, on the stability and reactivity of the alkylcobalt(III) intermediates. The activation of C(sp 2 )–X bonds (aromatic halides) has been observed from mono‐ or bi‐dentate electrogenerated cobalt(I) complexes like those obtained in DMF or acetonitrile mixed with pyridine as cosolvent. In such media, the oxidative addition of cobalt(I) on the C(sp 2 )–X bond competes with the disproportionation of very instable electrogenerated cobalt(I). Aromatic iodides, bromides, and chlorides undergo cobalt‐catalyzed electroreductive coupling with, namely, allyl and vinyl acetates, allyl ethers, olefins. The preparation of stable arylzinc compounds is also achieved in mild conditions. The mechanistic aspects of the reactions between aromatic halides and electrogenerated cobalt(I) have been extensively explored by electroanalytical techniques. The oxidative addition between ArX and cobalt(I) yields arylcobalt(III) intermediates which are immediately reduced into arylcobalt(II) complexes, which are the species responsible for the transmetalation with Zn(II) salts in the formation or arylzincs, or undergo an additional reduction step to yield arylcobalt(I), prone to engage in a new oxidative addition.

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Electrocarboxylation of chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline

Cited by 17 publications

References 28 publications

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

Electrochemistry of Organocobalt Compounds

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