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Novel Studies of Organic Electrosynthesis

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Electrochemistry".

Deadline for manuscript submissions: 31 March 2025 | Viewed by 2109

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Special Issue Information

Dear Colleagues,

Organic synthesis arguably represents the most important discipline for the bottom-up assembly and late-stage diversification of molecular compounds with transformative applications to inter alia medicinal chemistry, drug development, and material sciences, as well as the chemical and pharmaceutical industries. The complexity of electrochemistry and the physical properties of electrons are extraordinary and very different from other chemical reagents. Furthermore, the equipment needed to practice electrosynthesis has become readily available only since the early 1900s. These are the barriers that have prevented the acceptance of molecular electrosynthesis until very recently. Particularly, organic electrochemistry has, in recent years, overcome some of its previous limitations as a niche technique.

The pioneering contributions of Faraday’s hydrolysis of acetic acid, Kolbe’s electrochemical decarboxylative dimerization, Hickeling’s proposal of potential-controlled electrolysis, Simon’s fluorination process, Monsanto’s adiponitrile processes, Yoshida’s concept of electroauxiliaries, Steckan’s indirect electrolysis, BASF Lysmeral process (paired electrolysis), and the production of lead tetra-ethyl anti-knock compounds have enabled electrosynthesis to gain significant momentum for sustainable electro-organic syntheses.

The resurgence of this strategy has received great attention as a powerful green tool for synthesis, affording less waste production, less chemicals spent, and often fewer reaction steps than conventional methods. Functional group interconversion and C–C bond generation by the imposition of a proper electrode potential is essentially what lies behind organic electrosynthesis processes. Paired electrochemical reaction, indirect electrosynthesis, electrochemical microreactors, and the use of ionic liquids are some of the highlighted means that contribute to optimization of the overall process. The necessity to use specific organic solvents, combined with supporting electrolytes, is one of the main limitations to be overcome to render the electrochemical process more economically feasible when compared to non-electrochemical processes. Numerous examples from the bench scale to industrial routes, including contributions of organic electrosynthesis to green chemistry, are expected to be well covered throughout this Special Issue. Thus, we focus on the following topics:

  • Anodic functionalization of organic compounds;
  • Cathodic conversion of organic compounds;
  • Electrogenerated acids;
  • Electrogenerated bases;
  • Ionic liquids (ILs);
  • Indirect electrosynthesis;
  • Industrial electrosynthesis;
  • Dual electrocatalysis.

Prof. Dr. César Augusto Correia de Sequeira
Guest Editor

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Keywords

  • organic electrosynthesis
  • microreactors
  • modern redox mediators
  • organic reactions
  • room temperature ionic liquids (RTILs)
  • production plants design
  • bipolar/monopolar charge flow

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Published Papers (2 papers)

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Research

18 pages, 8563 KiB  
Article
The Comparison of Catalytic Activity of Carbimazole and Methimazole on Electroreduction of Zinc (II) in Chlorates (VII): Experimental and Molecular Modelling Study
by Jolanta Nieszporek, Tomasz Pańczyk and Krzysztof Nieszporek
Molecules 2024, 29(15), 3455; https://doi.org/10.3390/molecules29153455 - 23 Jul 2024
Viewed by 659
Abstract
With the help of electrochemical methods, including CV and EIS, the influence of methimazole, carbimazole, and the concentration of the supporting electrolyte on the kinetics and mechanism of zinc electroreduction on a mercury electrode was compared and analyzed. Moreover, molecular dynamics simulations of [...] Read more.
With the help of electrochemical methods, including CV and EIS, the influence of methimazole, carbimazole, and the concentration of the supporting electrolyte on the kinetics and mechanism of zinc electroreduction on a mercury electrode was compared and analyzed. Moreover, molecular dynamics simulations of zinc/carbimazole and zinc/methimazole solutions were carried out to determine the effect of drugs on the hydration sphere of Zn2+ ions. It was shown that the electroreduction of Zn2+ in the presence of methimazole and carbimazole occurs in two steps and the first one determines the kinetics of the entire process. The presence of both drugs in the solution and the increase in the concentration of the supporting electrolyte reduce the degree of hydration of the depolarizer ions and the hydration of the electrode surface, what is a factor favoring the rate of electroreduction. Based on theoretical studies, the formation of stable complexes between Zn2+ and the molecules of both drugs in a solution was considered unlikely. However, active complexes can be formed between depolarizer ions and molecules adsorbed at the electrode surface. They constitute a bridge facilitating charge exchange during the electrode reaction, revealing the catalytic abilities of methimazole and carbimazole. In the range of cdrug ≤ 1 × 10−3 mol dm−3, carbimazole is a better catalyst, whereas in the range of cdrug ≥ 5 × 10−3 mol dm−3, it is methimazole. The effectiveness of both compounds in catalyzing the first stage of the electrode reaction increases with the increase in the NaClO4 concentration. Full article
(This article belongs to the Special Issue Novel Studies of Organic Electrosynthesis)
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16 pages, 5174 KiB  
Article
Electrochemical Synthesis of the In Human S-oxide Metabolites of Phenothiazine-Containing Antipsychotic Medications
by Ridho Asra, Aigul Erbosynovna Malmakova and Alan M. Jones
Molecules 2024, 29(13), 3038; https://doi.org/10.3390/molecules29133038 - 26 Jun 2024
Cited by 1 | Viewed by 1175
Abstract
The tractable preparation of Phase I drug metabolites is a critical step to understand the first-pass behaviour of novel chemical entities (NCEs) in drug discovery. In this study, we have developed a structure–electroactivity relationship (SeAR)-informed electrochemical reaction of the parent 2-chlorophenothiazine and the [...] Read more.
The tractable preparation of Phase I drug metabolites is a critical step to understand the first-pass behaviour of novel chemical entities (NCEs) in drug discovery. In this study, we have developed a structure–electroactivity relationship (SeAR)-informed electrochemical reaction of the parent 2-chlorophenothiazine and the antipsychotic medication, chlorpromazine. With the ability to dial-in under current controlled conditions, the formation of S-oxide and novel S,S-dioxide metabolites has been achieved for the first time on a multi-milligram scale using a direct batch electrode platform. A potential rationale for the electrochemical formation of these metabolites in situ is proposed using molecular docking to a cytochrome P450 enzyme. Full article
(This article belongs to the Special Issue Novel Studies of Organic Electrosynthesis)
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