Reduction of aliphatic bromoesters

Inesi, Achille; Zeppa, A.; Zeuli, E.

doi:10.1016/0022-0728(82)85070-5

Cited by 14 publications

(5 citation statements)

References 16 publications

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“…2d). In agreement with earlier studies, 53,54 the reduction of α-bromoester 4a with strong EWG (CO 2 Me) adjacent to the C-Br bond required significantly less energy than the reduction of bromides 4b and 4c with EWG (CO 2 Me and CN, respectively) where the C-Br bond is separated by an additional carbon atom. This trend also correlates with the lower bond dissociation energy for 4a compared with that for aliphatic halides without strong EWG near C-Hal bond.…”

Section: Resultssupporting

confidence: 91%

Synthesis of Dimeric Molecules via Ag-Catalyzed Electrochemical Homocoupling of Organic Bromides Paired with Electrooxidation of Urea

Medvedev

Steksova

Medvedeva

et al. 2020

J. Electrochem. Soc.

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We present a sacrificial anode-free approach to reductive homocoupling of organohalides that does not require a co-catalyst. In this approach, a divided electrochemical cell with aprotic and aqueous compartments separated by an anion exchange membrane enables coupling of the cathodic homocoupling reaction with anodic oxidation of urea. We show that, in contrast with traditional one-compartment cells relying on sacrificial anodes, the proposed cell configuration maintains stable cell voltage in the course of galvanostatic electrolysis. A synthetic potential of this method was assessed using a series of 13 organic bromides that demonstrated a strong dependence of the reaction outcome on the structure of the organic substrate, more specifically, the dissociation energy of the C–Br bond and the redox properties of formed radicals, which are discussed in detail. While not being suitable for the synthesis of byarylstructures, this method is excellent for C(sp3)-C(sp3) coupling to corresponding dimeric products with up to quantitative yields. Simultaneous electrochemical treatment of nitrogenous waste in the adjacent half-cell provides an additional incentive for wide adaptation of this sustainable synthetic approach.

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Section: Resultssupporting

confidence: 91%

Synthesis of Dimeric Molecules via Ag-Catalyzed Electrochemical Homocoupling of Organic Bromides Paired with Electrooxidation of Urea

Medvedev

Steksova

Medvedeva

et al. 2020

J. Electrochem. Soc.

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“…Reaction (6) in Scheme 1 shows the reduction of 4 to its radical-anion (4 Å ). As implied by the cyclic voltammograms for 1 and 4 seen in Fig.…”

Section: Controlled-potential Electrolysis Of Ethyl 2-bromo-3-(3 0 ; mentioning

confidence: 99%

“…In a later investigation of the electrochemistry of several halogenated ethyl acetates, Baizer and Chruma [5] demonstrated that direct reduction of ethyl bromoacetate at mercury is a two-electron process which leads to formation of the ethoxycarbonylmethyl anion; once produced, this anion engages in non-electrochemical reactions to form ethyl acetate, diethyl succinate, 1,2,3-cyclopropane tricarboxylic acid triethyl ester, 1,2,3-propanetricarboxylic acid triethyl ester, and diethyl fumarate. Inesi et al [6] probed the direct reduction of several bromoesters at mercury and glassy carbon cathodes and reported the formation of the corresponding hydrogenated esters as well as unsaturated products that arise via elimination of a molecule of hydrogen bromide. In addition, a-and b-bromoesters were observed to afford dimeric products, and reduction of the former family of compounds was shown to proceed via both unbrominated and brominated carbanions as intermediates [7].…”

Section: Introductionmentioning

confidence: 99%

Direct electrochemical reduction of a bromo-propargyloxy ester at vitreous carbon cathodes in dimethylformamide

Esteves

Goken

Klein

et al. 2003

Journal of Electroanalytical Chemistry

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“…The electrochemical reduction conditions of the solution containing 1 may generate an EGB, which reacts with 1 to produce anionic A . At the stage of the generation of the EGB, the reduction of 1 may generate an enolate ion such as E or F , which might serve as EGB, although other sources of EGBs cannot be denied [ 30 – 31 ]. Intermediate A may combine with 1 to produce B , which may react with the EGB or another molecule A to produce C , releasing HCl.…”

Section: Resultsmentioning

confidence: 99%

Electrogenerated base-promoted cyclopropanation using alkyl 2-chloroacetates

Matsumoto¹,

Hayashi²,

Hamasaki³

et al. 2022

Beilstein J. Org. Chem.

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The electrochemical reduction conditions of the reaction of alkyl 2-chloroacetates in Bu4NBr/DMF using a divided cell equipped with Pt electrodes to produce the corresponding cyclopropane derivatives in moderate yields were discovered. The reaction conditions were optimized, the scope and limitations, as well as scale-up reactions were investigated. The presented method for the electrochemical production of cyclopropane derivatives is an environmentally friendly and easy to perform synthetic procedure.

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Reduction of aliphatic bromoesters

Cited by 14 publications

References 16 publications

Synthesis of Dimeric Molecules via Ag-Catalyzed Electrochemical Homocoupling of Organic Bromides Paired with Electrooxidation of Urea

Synthesis of Dimeric Molecules via Ag-Catalyzed Electrochemical Homocoupling of Organic Bromides Paired with Electrooxidation of Urea

Direct electrochemical reduction of a bromo-propargyloxy ester at vitreous carbon cathodes in dimethylformamide

Electrogenerated base-promoted cyclopropanation using alkyl 2-chloroacetates

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