Cathodic reductive coupling of methyl cinnamate on boron-doped diamond electrodes and synthesis of new neolignan-type products

Kojima, Taiki; Obata, Rika; Saito, Tsuyoshi; Einaga, Yasuaki; Nishiyama, Shigeru

doi:10.3762/bjoc.11.21

Cited by 22 publications

(14 citation statements)

References 16 publications

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“…[13] and oximes, [7a] the reductive coupling of cinnamates, [14] and the reductive formation of nitrones. [15] During the course of investigating the cathodic reduction of ketones on BDD electrodes, we unexpectedly discovered a cleavage of the acyl-carbon bond in phenylacetone derivative 1 a to give benzoic acid 2 a (Scheme 1).…”

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confidence: 99%

Oxidative Cleavage of the Acyl‐Carbon Bond in Phenylacetone with Electrogenerated Superoxide Anions

et al. 2018

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An oxidative cleavage reaction of the acyl−carbon bond in phenylacetone derivatives under cathodic reduction is reported. This particular transformation is driven by the cathodic reduction of dissolved molecular oxygen to superoxide anions. Various cathode materials were examined, and we discovered that boron‐doped diamond (BDD) enables highly efficient molecular conversion, owing to BDD's outstanding electrochemical property for utilizing the small amounts of molecular oxygen effectively. The scope of the reaction is broad and can be applied to a variety of substrates, ranging from ketones to esters and amides. As an electric current is directly employed to generate the superoxide anion, the reaction is metal‐ and catalyst‐free. Electro‐organic synthesis using the carbon‐based BDD electrode thus provides access to sustainable molecular transformations.

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confidence: 99%

Oxidative Cleavage of the Acyl‐Carbon Bond in Phenylacetone with Electrogenerated Superoxide Anions

et al. 2018

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“…Therefore, it is suggested that the intermediate A is not generate sufficiently in the absence of H 2 O, which results in a quite low yield of 2 a . The effect of adding H 2 O into electrolyte solution has been reported in previous reports: an oxidative cross‐coupling of aryls on the BDD anode and a reductive coupling of methyl cinnamate on the BDD cathode . The electrolysis in aprotic solvents resulted in a complete recovery of 1 a (Table , entries 3 and 4).…”

Section: Methodsmentioning

confidence: 54%

“…The effect of adding H 2 O into electrolyte solution has been reported in previous reports: an oxidative cross-coupling of aryls on the BDD anode [24] and a reductive coupling of methyl cinnamate on the BDD cathode. [10] The electrolysis in aprotic solvents resulted in a complete recovery of 1 a ( Table 2, entries 3 and 4). mole of 1 a), H-shaped divided cell, rt.…”

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confidence: 99%

Electrochemical Pinacol Coupling of Acetophenone Using Boron‐Doped Diamond Electrode

et al. 2019

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An electrochemical pinacol coupling reaction of acetophenone using a boron‐doped diamond (BDD) electrode has been reported. This transformation is driven by the one‐electron reduction of acetophenone on the BDD cathode, followed by an intermolecular radical coupling. Owing to the BDD's outstanding electrochemical properties, the pinacol‐type compound has been obtained in good conversion yield. The roles of a supporting electrolyte and solvent were addressed; (1) lithium ions contribute to increase in the reactivity of the radical intermediate. (2) Addition of water promotes the electron transfer process at the BDD surface. The reaction is relatively tolerant to para‐substituted acetophenone derivatives. Since electric current is directly employed as reducing reagents to generate a radical intermediate, the reaction is metal‐free, sustainable, and inherently safe.

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“…Besides CO 2 reduction also other cathodic conversions at BDD electrodes are reported. Kojima and co‐workers investigated the reductive coupling of methyl cinnamates at BDD electrodes (Scheme ) …”

Section: Unique Reactivity Of Boron‐doped Diamond Electrodesmentioning

confidence: 99%

“…After separation, the racemate was used as starting material for the lignin synthesis. Although other electrode systems were tested, BDD led to the best result with regard to yield and selectivity …”

Section: Unique Reactivity Of Boron‐doped Diamond Electrodesmentioning

confidence: 99%

Use of Boron‐Doped Diamond Electrodes in Electro‐Organic Synthesis

2019

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Boron‐doped diamond is a powerful and innovative material with outstanding properties, experiencing a strongly emerging interest in the chemical society as electrode material. BDD is generally used as a p‐doped semiconductor that can be applied for the disinfection and detoxification of waste‐water since very reactive intermediates can be formed. Besides this destructive performance of BDD electrodes the extraordinary characteristics can also be successfully employed in electro‐synthetic transformations. The performance is usually beyond and much superior to common electrode materials. A key step for the broad interdisciplinary field of application of this particular electrode material is the direct generation of oxyl radicals by electrochemical oxidation. The intention of this mini‐review is to provide the reader a brief overview of the current state of research and to illustrate the different fields of application. The methods applied are critically reviewed.

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Cathodic reductive coupling of methyl cinnamate on boron-doped diamond electrodes and synthesis of new neolignan-type products

Cited by 22 publications

References 16 publications

Oxidative Cleavage of the Acyl‐Carbon Bond in Phenylacetone with Electrogenerated Superoxide Anions

Oxidative Cleavage of the Acyl‐Carbon Bond in Phenylacetone with Electrogenerated Superoxide Anions

Electrochemical Pinacol Coupling of Acetophenone Using Boron‐Doped Diamond Electrode

Use of Boron‐Doped Diamond Electrodes in Electro‐Organic Synthesis

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