Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime DOI Open Access
Jiawei Kang, Peisen Liao,

Runan Xiang

и другие.

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Язык: Английский

Overcoming Challenges in Electrosynthesis Using High‐Throughput Electrochemistry: Hypervalent Iodine‐Mediated Phenol Dearomatization, a Case Study DOI Creative Commons
Antoine Juneau,

Marzieh Abdolhosseini,

Camille Rocq

и другие.

ChemElectroChem, Год журнала: 2024, Номер 11(13)

Опубликована: Май 2, 2024

Abstract Despite many recent efforts, the field of organic electrosyn‐thesis faces important challenges due to intricate nature heterogeneous redox processes, wide parameter space be explored and lack standardized methods. To overcome these limitations, we developed a cost‐effective high‐throughput electrochemical (HTE) reactor capable running 24 individually controlled parallel reactions. This system allows rapid testing parameters on given reaction, assessing not only yield but also reproducibility. Using hypervalent iodine‐mediated dearomatization phloretic acid as demonstration HTE capabilities, ran more than 200 electrosyntheses in different experimental conditions demonstrate effect such total charge transferred, current, electrode materials, electrolyte formulation concentration, mediator concentration technique oxidation. Notably, this report demonstrates that while catalytic amounts iodine can used successfully, reproducibility may affected, which calls for cautious approach when developing similar transformations. cyclic voltammetry, density functional theory, chronopotentiometry, Raman spectroscopy, shed light causes issue.

Язык: Английский

Процитировано

6
Electrolysis in thin layer: A technique for electroanalytical and electrosynthetic applications DOI

Buwanila T. Punchihewa,

Lida Khalafi,

Mohammad Rafiee

и другие.

Current Opinion in Electrochemistry, Год журнала: 2024, Номер 44, С. 101445 - 101445

Опубликована: Фев. 7, 2024

Язык: Английский

Процитировано

5
A guide to troubleshooting metal sacrificial anodes for organic electrosynthesis DOI Creative Commons
Skyler D. Ware,

Wendy Zhang,

Weiyang Guan

и другие.

Chemical Science, Год журнала: 2024, Номер 15(16), С. 5814 - 5831

Опубликована: Янв. 1, 2024

Sacrificial anodes enable reductive electrosynthesis but can inadvertently limit the conditions compatible with organic reactions. Addressing challenges that arise at sacrificial improve yields and streamline reaction optimization.

Язык: Английский

Процитировано

5
Zinc and manganese redox potentials in organic solvents and their influence on nickel-catalyzed cross-electrophile coupling DOI Creative Commons
Zhi-Ming Su, Ruohan Deng, Shannon S. Stahl

и другие.

Опубликована: Май 27, 2024

Zinc and manganese are widely used as reductants in synthetic methods, such nickel-catalyzed cross-electrophile coupling (XEC) reactions, but their redox potentials unknown organic solvents. Here, we show how open-circuit potential measurements may be to determine the thermodynamic of Zn Mn different solvents presence common reaction additives. The impact these is analyzed for a pair Ni-catalyzed each showing preference one two reductants. N-alkyl-2,4,6-triphenylpyridinium reagents (Katritzky salts) with aryl halides then compared under chemical conditions, using or reductants, electrochemical performed at applied corresponding reduction optimized achieve maximum yield. collective results illuminate important role reductant XEC reactions.

Язык: Английский

Процитировано

5
Reaction and transport co-intensification enhanced continuous flow electrocatalytic aminoxyl-mediated oxidation of sterol intermediates by 3D porous framework electrode DOI

Suiqin Li,

Chun Li, Kai Li

и другие.

Chemical Engineering Journal, Год журнала: 2022, Номер 446, С. 136659 - 136659

Опубликована: Май 7, 2022

Язык: Английский

Процитировано

19
Electrochemical synthesis of sulfonyl fluorides from sulfonyl hydrazides DOI

Jin Kyu Park,

Jonghoon Oh,

Sunwoo Lee

и другие.

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(13), С. 3407 - 3413

Опубликована: Янв. 1, 2022

The reaction of sulfonyl hydrazides and Et 3 N·3HF under electrochemical conditions afforded the corresponding fluorides in good yields.

Язык: Английский

Процитировано

18
Electrosynthesis and Microanalysis in Thin Layer: An Electrochemical Pipette for Rapid Electrolysis and Mechanistic Study of Electrochemical Reactions DOI Creative Commons

Buwanila T. Punchihewa,

Vidit Minda, William G. Gutheil

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Сен. 5, 2023

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

Язык: Английский

Процитировано

11
Catalyst- and Additive-Free Electrochemical CO2 Fixation into Morita–Baylis–Hillman Acetates DOI
Giulio Bertuzzi, Marco Bandini, Andrea Brunetti

и другие.

Synthesis, Год журнала: 2023, Номер 55(18), С. 3047 - 3055

Опубликована: Фев. 6, 2023

Abstract The electrochemical carboxylation of Morita–Baylis–Hillman (MBH) acetates with CO2 is presented. process proceeds in the absence transition-metal catalysts and relies on cathodic reduction MBH to generate nucleophilic anions that are able trap low-pressure CO2. Valuable succinate derivatives obtained (20 examples) high yields (up 90%) excellent functional group tolerance. A remarkable substrate-controlled (electronic nature) regioselectivity transformation documented along a mechanistic rationale based control experiments.

Язык: Английский

Процитировано

10
Disulfides as versatile starting reagents: effective sulfonylation of alkenes with disulfides under electrochemical conditions DOI
Olga M. Mulina, Mikhail M. Doronin, Liang‐Nian He

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(14), С. 3559 - 3566

Опубликована: Янв. 1, 2023

The unexpectedly effective use of disulfides as S-partners in electrochemical C–S coupling is demonstrated.

Язык: Английский

Процитировано

10
A Voltage-Controlled Strategy for Modular Shono-Type Amination DOI
Siyuan Su, Yahui Guo, Bryan Parnitzke

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 28663 - 28668

Опубликована: Окт. 14, 2024

Shono-type oxidation to generate functionalized heterocycles is a powerful method for late-stage diversification of relevant pharmacophores; however, development beyond oxygen-based nucleophiles remains underdeveloped. The limited scope can often be ascribed constant current electrolysis resulting in potential drifts that oxidize desired nucleophilic partner. Herein, we report voltage-controlled strategy selectively broad substrates, enabling modular C-N bond formation from protected amine nucleophiles. We implement an electroanalytically guided workflow using cyclic voltammetry (CV) and differential pulse (DPV) identify potentials across range heterocyclic substrates. Controlled (CPE) generates α-functionalized products moderate good yields carbamate-, sulfonamide-, benzamide-derived importance voltage control further exemplified through systematic study comparing our developed CPE (CCE) protocols. Voltage-guided CCE traditionally optimized reveal the maintaining high selectivity over scope; case with morpholine-derived substrate illustrates negative impact drifting under CCE. Sulfonamide drugs, which have significant overlap model are rendered competent CPE. Lastly, sequential C-O functionalization difunctionalized pyrrolidines broadening utility this reaction.

Язык: Английский

Процитировано

4