Electrosynthesis Reactions Research Articles

An Electrochemical Pipette for Study of the Drug Metabolites

The similarity between electrochemical and biological redox reactions, particularly in the realm of CYP450-catalyzed oxidation, provides the basis for using electrochemistry to simulate drug metabolism and to synthesize complex drug candidates. The tunability of electrochemical reactions, mild reaction conditions, and the avoidance of toxic reagents are the characteristics of electrochemical reactions in mimicking enzymatic drug metabolites. The acquired insights from these techniques can be used to assess the metabolites' potential toxicity and pharmacological properties. These features along with insights from electrochemical drug metabolism enable chemists to accomplish transformations on complex, functionalized molecules with high selectivity and hold great promise for improving the processes used for pharmaceutical synthesis. An instance is exemplified by acetaminophen (APAP), for which adverse side effects have been ascribed to the oxidative generation of a metabolite known as N-acetyl-p-benzoquinone imine (NAPQI). This well-established area showcased impressive examples of the ability of electrochemistry to replicate phase I and II APAP metabolism reactions. Yet, it is often limited to an analytical scale, hampering comprehensive characterization and complete metabolic behavior elucidation. The synthetic scale preparation of metabolites for quantitative analysis and their further studies is a valuable complementary approach to EC-MS techniques.Recently, we designed a thin layer electrode that the electrode can be pulled and pushed, like a pipette inside a glass tube, allowing for the taking in and expelling of the sample into and from the thin layer, respectively.1 The thin layer electrochemical pipette allows rapid electrolysis on a microscale making it suitable for the study of the products or intermediates of drug metabolites. The required time for electrolysis or voltammetric experiments in this TLE is in order of minutes, shorter than traditional electrolysis cells, and longer than many of the electroanalytical techniques. This allows us to detect and investigate the drug metabolites with a minute scale half-life. Herein, we showcase the utilization of microscale electrolysis to investigate drug metabolites, specifically elucidating the oxidation pathways of paracetamol and acebutolol drugs using thin-layer electrolysis (TLE) and cyclic voltammetry (CV). We successfully identified well-defined redox peaks of p-benzoquinone and hydroquinone, which remain undetectable through conventional electrolysis, whether in short or extended durations. Additionally, employing a microelectrode in the TLE facilitates the real-time examination of concentration profiles for both redox-active and inactive components involved in electrosynthesis reactions, allowing us to extract valuable kinetic information. Conducting CV experiments within the framework of (TLE) not only yielded detailed electrochemical insights into the mechanisms but also produced micromole-scale products, which can be fully characterized via chromatographic or spectroscopic methods.1. B.T. Punchihewa, V. Minda, W.G. Gutheil, M. Rafiee, Electrosynthesis and Microanalysis in Thin Layer: An Electrochemical Pipette for Rapid Electrolysis and Mechanistic Study of Electrochemical Reactions. Angew. Chem. Int. Ed. 2023, 62, e202312048.

Electrosynthesis of Glyoxylic Acid By Electrochemical Reduction of Oxalic Acid and Oxidation of Glyoxal inside Co-Laminar Flow Cells

This study investigates the simultaneous electrosynthesis of glyoxylic acid through electrochemical reduction of oxalic acid and oxidation of glyoxal inside a co-laminar flow reactor. This system offers specific advantages over traditional beaker cells including: continuous operation and controlled mixing of products.This study involves a systematic exploration of operating conditions such as flow rate, applied potential, current density, electrode gap and influence of specific electrocatalysts. These operating conditions are varied while the yield and current efficiency of the cell are measured. In this way, the optimum conditions for electrosynthesis of glyoxylic acid are determined and insight into the efficiency of other electrosynthesis reactions is obtained.

Influence of Complex Multiphasic Flow on the Thiuram Electrosynthesis in a Microchannel Reactor.

As an important sustainable method for chemical synthesis, organic electrosynthesis experienced a renaissance in recent years for its excellent atom economy. Although microchannel reactors have been proposed to advanced electrosynthesis devices to obtain low energy cost and high reaction performance, the complex multiphasic flow in the electrochemical microchannels are very less reported and the effects of flow condition on the electrosynthesis reaction are less reported. Taking the electrosynthesis of tetraethyl thiuram disulfide (TETD) as a typical case, we developed a visualized electrochemical microchannel reactor equipped with fluorine-doped tin oxide (FTO) loaded glass electrode to investigate the gas-liquid-liquid triple phase flow pattern and the main factors influenced the response current at certain applied cell voltage. The gas-liquid-liquid hybrid flow with low gas hold-up and high liquid flow rate was found crucial for preventing coverage of TETD on the electrode, which provided 23.1 % low current attenuation ratio at 3.0 V cell voltage. The research not only exhibited the complex evolution mechanism of the response current, but also showed the importance of flow condition control for balancing the work efficiency and energy consumption of electrosynthesis process.

Single-Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis.

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single-electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single-atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe-SA@NC as an advanced redox mediator to try to change this situation. Fe-SA@NC was synthesized using an encapsulation-pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C-C/C-X bonds. Moreover, Fe-SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro-oxidative ring-opening transformation of cyclopropyl amides. In this new reaction system, Fe-SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram-scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry.

Single‐Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis

AbstractHomogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single‐electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single‐atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe‐SA@NC as an advanced redox mediator to try to change this situation. Fe‐SA@NC was synthesized using an encapsulation‐pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C−C/C−X bonds. Moreover, Fe‐SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro‐oxidative ring‐opening transformation of cyclopropyl amides. In this new reaction system, Fe‐SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram‐scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry.

Automated electrosynthesis reaction mining with multimodal large language models (MLLMs).

Leveraging the chemical data available in legacy formats such as publications and patents is a significant challenge for the community. Automated reaction mining offers a promising solution to unleash this knowledge into a learnable digital form and therefore help expedite materials and reaction discovery. However, existing reaction mining toolkits are limited to single input modalities (text or images) and cannot effectively integrate heterogeneous data that is scattered across text, tables, and figures. In this work, we go beyond single input modalities and explore multimodal large language models (MLLMs) for the analysis of diverse data inputs for automated electrosynthesis reaction mining. We compiled a test dataset of 65 articles (MERMES-T24 set) and employed it to benchmark five prominent MLLMs against two critical tasks: (i) reaction diagram parsing and (ii) resolving cross-modality data interdependencies. The frontrunner MLLM achieved ≥96% accuracy in both tasks, with the strategic integration of single-shot visual prompts and image pre-processing techniques. We integrate this capability into a toolkit named MERMES (multimodal reaction mining pipeline for electrosynthesis). Our toolkit functions as an end-to-end MLLM-powered pipeline that integrates article retrieval, information extraction and multimodal analysis for streamlining and automating knowledge extraction. This work lays the groundwork for the increased utilization of MLLMs to accelerate the digitization of chemistry knowledge for data-driven research.

In situ electrosynthesis of quinone-based redox-active molecules coupling with high-purity hydrogen production.

Clean hydrogen production via conventional water splitting involves sluggish anodic oxygen evolution, which can be replaced with more valuable electrosynthesis reactions. Here, we propose one novel strategy for coupling in situ organic electrosynthesis with high-purity hydrogen production. A benzoquinone-derivative disodium 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron)-o1 and a naphthoquinone-derivative 2,6,8-trismethylaminemethylene-3,5-dihydroxy-1,4-naphthoquinone (TANQ) were in situ electrosynthesized and directly used in a flow battery without any further purification treatment. Constant, simultaneous production of TANQ and hydrogen was demonstrated for 61 hours, while stable charge-discharge capacities were retained for 1000 cycles. The work provided a new avenue for achieving in situ redox-active molecule synthesis and high-purity hydrogen.

Tuning Surface Reactivity and Electric Field Strength via Intermetallic Alloying.

Many electrosynthesis reactions, such as CO2 reduction to multicarbon products, involve the formation of dipolar and polarizable transition states during the rate-determining step. Systematic and independent control over surface reactivity and electric field strength would accelerate the discovery of highly active electrocatalysts for these reactions by providing a means of reducing the transition state energy through field stabilization. Herein, we demonstrate that intermetallic alloying enables independent and systematic control over d-band energetics and work function through the variation of alloy composition and oxophilic constituent identity, respectively. We identify several intermetallic phases exhibiting properties that should collectively yield higher intrinsic activity for CO reduction compared to conventional Cu-based electrocatalysts. However, we also highlight the propensity of these alloys to segregate in air as a significant roadblock to investigating their electrocatalytic activity.

Electrosynthesis and Microanalysis in Thin Layer: An Electrochemical Pipette for Rapid Electrolysis and Mechanistic Study of Electrochemical Reactions.

Electrochemistry represents unique approaches for the promotion and mechanistic study of chemical reactions and has garnered increasing attention in different areas of chemistry. This expansion necessitates the enhancement of the traditional electrochemical cells that are intrinsically constrained by mass transport limitations. Herein, we present an approach for designing an electrochemical cell by limiting the reaction chamber to a thin layer of solution, comparable to the thickness of the diffusion layer. This thin layer electrode (TLE) provides a modular platform to bypass the constraints of traditional electrolysis cells and perform electrolysis reactions in the timescale of electroanalytical techniques. The utility of the TLE for electrosynthetic applications benchmarked using NHPI-mediated electrochemical C-H functionalization. The application of microscale electrolysis for the study of drug metabolites was showcased by elucidating the oxidation pathways of the paracetamol drug. Moreover, hosting a microelectrode in the TLE, was shown to enable real-time probing of the profiles of redox-active components of these rapid electrosynthesis reactions.

Wireless Electrochemical Reactor for Accelerated Exploratory Study of Electroorganic Synthesis.

Electrosynthesis is an emerging tool to construct value-added fine chemicals under mild and sustainable conditions. However, the complex apparatus required impedes the facile development of new electrochemistry in the laboratory. Herein, we proposed and demonstrated the concept of wireless electrochemistry (Wi-eChem) based on wireless power transfer technology. The core of this concept is the dual-function wireless electrochemical magnetic stirrer that provides an electrolysis driving force and mixing simultaneously in a miniaturized form factor. This Wi-eChem system allowed electrochemists to execute electrochemical reactions in a manner similar to traditional organic chemistry without handling wire connections. The controllability, reusability, and versatility were validated with a series of modern electrosynthesis reactions, including electrodecarboxylative etherification, electroreductive olefin-ketone coupling, and electrochemical nickel-catalyzed oxygen atom transfer reaction. Its remarkably simplified operation enabled its facile integration into a fully automated robotic synthesis platform to achieve autonomous parallel electrosynthesis screening.

Electrosynthesis and Microanalysis in Thin Layer: An Electrochemical Pipette for Rapid Electrolysis and Mechanistic Study of Electrochemical Reactions

Electrochemistry represents unique approaches for the promotion and mechanistic study of chemical reactions and has garnered increasing attention in different areas of chemistry. This expansion necessitates the enhancement of the traditional electrochemical cells that are intrinsically constrained by mass transport limitations. Herein, we present an approach for designing an electrochemical cell by limiting the reaction chamber to a thin layer of solution, comparable to the thickness of the diffusion layer. This thin layer electrode (TLE) provides a modular platform to bypass the constraints of traditional electrolysis cells and perform electrolysis reactions in the timescale of electroanalytical techniques. The utility of the TLE for electrosynthetic applications benchmarked using NHPI‐mediated electrochemical C‐H functionalization. The application of microscale electrolysis for the study of drug metabolites was showcased by elucidating the oxidation pathways of the paracetamol drug. Moreover, hosting a microelectrode in the TLE, was shown to enable real‐time probing of the profiles of redox‐active components of these rapid electrosynthesis reactions.

Broadband Microwave Microfluidic Spectroscopy to Capture Product Evolution in Electrosynthesis Reactions

Electrosynthesis plays an important role in chemical manufacturing with over 2 billion dollars in annual sales worldwide of products such as chlor-alkali and aluminum. Synthesis with an electrochemical driving force can afford unique chemical products that are difficult to achieve with conventional synthesis techniques. Electrosynthesis can also provide a more sustainable alternative to energy-intensive processes. For example, the most profitable electro-organic synthesis in industry is adiponitrile production, a precursor to Nylon 6,6, and the electrochemical route consumes less energy than conventional thermochemical methods. However, electrosynthesis reaction mechanisms are often complex and involve multiple biproducts that are difficult to distinguish, limiting product yield and cost efficiency. Prior work involves characterization with techniques such as NMR spectroscopy, mass spectrometry, and optical spectroscopy to understand product evolution during the reaction. These methods tend not to capture intermolecular interactions between substances, which is important for understanding the influence of the dielectric environment on reaction outcomes.Here, we propose to analyze the dielectric environment of electrosynthesis reaction mixtures with on-chip broadband microwave microfluidic spectroscopy (MMS) from 40 kHz – 110 GHz (see attached figure). MMS has been implemented previously for capturing broadband fluid effects such as electric double layer formation, ionic conduction, ion pairing, and dipole relaxations in a single measurement. We want to use MMS to diagnose the interactions between species during an electrolysis reaction and correlate these interactions with specific electrochemical mechanisms. We plan to test our idea by analyzing a model reaction, namely the Shono oxidation of N-Boc pyrrolidine, which is a well-studied electrosynthesis reaction. The goal is to validate our method with a known electrosynthesis reaction mechanism, then extend the technique to systems with an unknown mechanism.We performed broadband MMS of the reaction mixture at different time points to capture product evolution during the electrolysis. Then, we calibrated the resulting S-parameters and fit the data to equivalent circuit models. The equivalent circuit parameters were correlated to signatures from specific entities in the product mixture and used to develop a picture of the evolving dielectric environment. After validating our models with known literature about the Shono oxidation mechanism, we plan to extend our technique to other electrolysis reactions with unknown mechanisms. The goal is to provide a high-throughput technique for identifying key species and interactions that influence the outcome of electrolysis reactions. Figure 1

Potential-Dependent Competitive Adsorption of Electrolytes Kinetically Inhibits High-Current Hydrogen Oxidation in Non-Aqueous Media

Performing electrochemical transformations in non-aqueous media can unlock new reactivities and selectivities unattainable in aqueous media. For instance, non-aqueous media (e.g. acetonitrile (MeCN), dimethylformamide (DMF), dimethylsulfoxide (DMSO)) allow the dissolution of organic compounds and enable water-incompatible organic electrosynthesis reactions. On the other hand, the lithium-mediated nitrogen reduction reaction (NRR) carried out electrochemically in tetrahydrofuran (THF) is one of the most promising routes towards electrifying the Haber-Bosch reaction and thus eliminating the need for hundreds of atmospheres of pressure and high temperatures. However, many cathodic non-aqueous electrochemical reactions either do not operate with well-defined anodic reactions (e.g. unproductive solvent and/or electrolyte oxidation) or are often coupled with the sacrificial oxidation of a dissolving metal electrode (e.g. magnesium, zinc). Hence, the development of a non-sacrificial anodic reaction is essential for engineering practical, sustainable non-aqueous electrochemical transformations. In this study, we investigate the hydrogen oxidation reaction (HOR) in a variety of non-aqueous solvents (MeCN, DMF, DMSO, THF) and buffers (AcO-/AcOH, Cl-/HCl, etc.) whose base serves as the proton acceptor for HOR. The reason why HOR can be sustainable is because it produces protons, which can be paired with a number of proton-demanding electro-reductions such as NRR, carbon dioxide reduction (CDR) to form oxalic acid or carboxylic acids, and more. Hydrogen is also stoichiometrically cheaper and less greenhouse-emitting than sacrificial metals, making HOR both cheaper and greener. First, we demonstrate a fabricated gas diffusion electrode (GDE) architecture that supports high H2 transport-limited current densities in non-aqueous solvents at ambient pressure. We find that the maximum HOR current density obtained is not H2 transport-limited but instead depends on the kinetics influenced by the pKa and steric profile of the buffer electrolytes present. By also varying the buffer electrolyte concentration and H2 partial pressure and conducting voltametric studies in the absence of H2, we demonstrate that the HOR current density reaches a maximum due to a competitive adsorption mechanism of the buffer electrolytes, limiting the surface concentration of adsorbed hydrogen atoms from H2 dissociative adsorption and thus inhibiting HOR. Based on these findings, we outline strategies for mitigating HOR inhibition via this competitive adsorption mechanism to unlock higher HOR current densities.

Understanding urea electro synthesis using layered perovskite NdBa0.25Sr0.75Co2O5+ δ cathode material

Urea production through an electro-synthetic approach emerges as a sustainable alternative compared to its conventional energy-intensive and polluting technologies. However, the advancement of the aforementioned technique is primarily impeded by existing inefficient electrocatalysts. Therefore, the rational design of the indispensable catalyst along with the unveiling of the reaction pathway through intermediate identification, would enable the utmost deployment of the proposed strategy. Herein, we prepared a non-noble layered perovskite NdBa0.25Sr0.75Co2O5+ δ using the citric acid-metal nitrate combustion method and utilized it as an electrocatalyst alongside CO2 and nitrite contaminants used as input sources for urea synthesis. The synthesized electrocatalyst proffered remarkable electrochemical performance for the above-stated urea electrosynthesis reaction with a yield rate of 6.66 µmol g−1 h−1 and Faradaic efficiency (F.E) of 9.5%, respectively, at − 1.04 V vs RHE optimized conditions. High-performance liquid chromatography analysis was performed for end-product quantification. The favourable urea formation could be attributable to the unique distribution of prevailing oxygen vacancies in the perovskite cathode material. The insights provided in the article unravel a novel paradigm for the use of layered perovskite materials in urea electrosynthesis.

Tuning the adsorption behaviors of non-noble electrocatalysts to boost valorization of 5-hydroxymethylfurfural

We demonstrate that NiCu oxide catalyst with low-coordinated surface sites facilitates the adsorption of 5-hydroxymethylfurfural (HMF) and hence exhibits good electrocatalytic performance towards HMF oxidation reaction (HMFOR).

Measurement and Experimental Procedures in Electrosynthesis Reaction for Low Molecular Weight Reactants

Measurement and Experimental Procedures in Electrosynthesis Reaction for Low Molecular Weight Reactants

Electrosynthesis of tetrabenzylthiuram disulfide via flow reactors

• Advanced flow electrosynthesis method of TBzTD is developed. • Main factors influenced the electrosynthesis reaction are carefully discussed. • The scaling-up of flow reactor via increasing electrode area is exhibited. • Circulation of aqueous solution is accomplished for high atomic economy. Tetrabenzylthiuram disulfide (TBzTD) is an environmentally friendly vulcanization accelerator, which has attracted much attention in recent years. In contrast to traditional synthesis technologies, which create stoichiometric sodium sulfate or sodium chloride waste salts, we carefully studied an electrosynthesis method of TBzTD based on flow reactors, which prevented the generation of salt. Two reactors with different electrode areas were used to implement the electrochemical oxidative coupling reaction of sodium dibenzyl dithiocarbamates, and effects of potential, current, electrode material, electrode distance, flow rate, concentration, and temperature on the yield and space time yield of TBzTD were carefully investigated. Almost 100% Faraday efficiency of the reaction was obtained at relatively optimized reaction condition and the highest yield of TBzTD reached 86%. Although the yield of TBzTD did not reach 100% in the electrosynthesis reaction, the circulation of aqueous phase demonstrated by a membrane separator assisted flow reaction system helped to accomplish fully conversion of initial amine and carbon disulfide and atomic economic synthesis of TBzTD.

Product identification and mechanism exploration of organic electrosynthesis using on-line electrochemistry-mass spectrometry

• An innovative EC-MS method was proposed to quickly optimize experimental conditions. • Quickly determine reaction selectivity of organic electrosynthesis. • EC-MS has potential application in flow chemistry due to its in-situ monitor. Though organic electrosynthesis has been used widely as a sustainable and green synthetic method for decades, the optimization of organic electrosynthesis reactions can be limited when product isolation and purification is a tedious and time-consuming process. An innovative electrochemistry-mass spectrometry method is proposed in this study to enhance experimental conditions and expedite reaction selectivity of organic electrosynthesis. The method can be used as a supplementary technology of cyclic voltammetry, providing an effective way to identify oxidation products and illustrate of reaction mechanism, and thus proves itself to be highly valuable in the field of organic electrosynthesis reaction monitoring. In conformity with the concept of green and sustainable synthetic strategy, no metal medium or complex supporting electrolytes are involved in the experiment.

METHODOLOGY OF «GREEN» CHEMISTRY IN THE SYNTHESIS OF SUBSTITUTED 2-AMINOPYRANES (PYRIDINE) -3-CARBONITRILE

Numerous studies in the chemistry of heterocyclic compounds today are devoted to solving environmental and economic problems (environmental pollution, irrational use of natural re-sources, etc.). This mini-review summarizes and analyzes the literature data of the last 10 years (2011-2021) on the «green» synthesis of structurally similar 2-aminopyrans (pyridine) -3-carboni-triles (polysubstituted, annelated with different types of articulation of rings, spirocyclic) contain-ing in the heteroring, substituent groups (functional analogs), identical in nature (CN, NH2) and position (at C2 -C3), are similar in production methods, formation routes. The main «green» ap-proach to the synthesis of 2-aminopyran (pyridine)-3-carbonitriles is multicomponent condensa-tion during thermal, ultrasonic, microwave activation, and electrolysis. Reagents in the synthesis of 2-aminopyran-3-carbonitriles are malononitrile, (di) carbonyl compounds (aromatic, alicyclic, aliphatic), phenols, hydroxynaphthols, in the case of 2-aminopyridine-3-carbonitriles -malonodi-nitrile, carbonyl compounds, aminating agents (ammonium acetate, aromatic and heterocyclic amines). Numerous studies devoted to the search for catalysts that can replace toxic catalysts (ali-phatic, heterocyclic amines), which are used repeatedly with the same effectiveness. Promising cat-alysts that meet these requirements have been found -nano-, nanomagnetic, organic, solid hetero-geneous catalysts (based on silicon oxide, titanium oxide, graphene). Much attention is paid to the selection of environmentally friendly solvents, available, cheap (water, ethanol), the use of ionic liquids. Electrochemical synthesis is recognized as «green» because toxic catalysts are replaced by electric current. A series of electrosynthesis reactions of annelated, spiro-fused, polyheteroatomi-cheterosystems obtained in the nanoscale range is presented. A large number of publications over the past decade have shown that the methodology of «green» chemistry provides a low-step, effi-cient, low-waste pathway for the synthesis of substituted 2-aminopyran (pyridine) -3-carbonitriles, which corresponds to the PASE (Pot-Atom-Step-Econiomic) principle. It should be noted that this path is not devoid of disadvantages, such as the use of expensive catalysts and complex hardware design. From a huge number of publications over the last decade on the synthesis of 2-aminopyran (pyridine) -3-carbonitriles, only those concerning the use of the methodology of «green» chemistry, the most significant and informative (21 publications) were selected.

Access to α,α-dihaloacetophenones through anodic C[dbnd]C bond cleavage in enaminones

We have developed a method to synthesize α,α-dihaloketones under electrochemical conditions. In this reaction, the Cl- or Br- is oxidized to Cl2 or Br2 at the anode, which undergoes two-step addition reactions with the N,N-dimethyl enaminone, and finally breaks CC of the N,N-dimethyl enaminone to generate α,α-dihaloketones. The electrosynthesis reaction can be conveniently carried out in an undivided electrolytic cell at room temperature. In addition, various functional groups are compatible with this green protocol which can be applied simultaneously to the gram scale without significantly lower yield.