Overcoming the limitations of Kolbe coupling with waveform-controlled electrosynthesis

Science, Год журнала: 2023, Номер 380(6640), С. 81 - 87

Опубликована: Апрель 6, 2023

The Kolbe reaction forms carbon-carbon bonds through electrochemical decarboxylative coupling. Despite more than a century of study, the has seen limited applications owing to extremely poor chemoselectivity and reliance on precious metal electrodes. In this work, we present simple solution long-standing challenge: Switching potential waveform from classical direct current rapid alternating polarity renders various functional groups compatible enables sustainable carbon-based electrodes (amorphous carbon). This breakthrough enabled access valuable molecules that range useful unnatural amino acids promising polymer building blocks readily available carboxylic acids, including biomass-derived acids. Preliminary mechanistic studies implicate role in modulating local pH around crucial acetone as an unconventional solvent for reaction.

Язык: Английский

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Electrochemical oxidative C(sp3)–H cross-coupling with hydrogen evolution

Nature Synthesis, Год журнала: 2023, Номер 2(3), С. 217 - 230

Опубликована: Фев. 16, 2023

Язык: Английский

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Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(50)

Опубликована: Авг. 22, 2023

Abstract Organic electrosynthesis has consistently aroused significant interest within both academic and industrial spheres. Despite the considerable progress achieved in this field, majority of electrochemical transformations have been conducted through utilization direct‐current (DC) electricity. In contrast, application alternating current (AC), characterized by its polarity‐alternating nature, remains infancy sphere organic synthesis, primarily due to absence a comprehensive theoretical framework. This minireview offers an overview recent advancements AC‐driven seeks elucidate differences between DC AC electrolytic methodologies probing into their underlying physical principles. These encompass ability preclude deposition metal catalysts, precision modulating oxidation reduction intensities, mitigation mass transfer processes.

Язык: Английский

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Programmed alternating current optimization of Cu-catalyzed C-H bond transformations

Science, Год журнала: 2024, Номер 385(6705), С. 216 - 223

Опубликована: Июль 11, 2024

Direct current (DC) electrosynthesis, which has undergone optimization over the past century, plays a pivotal role in variety of industrial processes. Alternating (AC) characterized by polarity reversal and periodic fluctuations, may be advantageous for multiple chemical reactions, but apparatus, principles, application scenarios remain underdeveloped. In this work, we introduce protocol programmed AC (pAC) electrosynthesis that systematically adjusts currents, frequencies, duty ratios. The representative pAC waveforms facilitates copper-catalyzed carbon-hydrogen bond cleavage cross-coupling difunctionalization reactions exhibit suboptimal performance under DC oxidation conditions. Moreover, observing catalyst dynamic variation diverse waveform applications provides mechanistic insight.

Язык: Английский

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Stirring‐Free Scalable Electrosynthesis Enabled by Alternating Current

Chemistry - A European Journal, Год журнала: 2023, Номер 29(18)

Опубликована: Янв. 3, 2023

Alternating current (AC) electrolysis is receiving increased interest as a versatile tool for mild and selective electrochemical transformations. This work demonstrates that AC can enable the concept of stirring-free reactor where periodic switch electrode polarity, inherent to AC, provides uniform across whole volume reactor. Such design implies straightforward approach scaling up electrosynthesis. was demonstrated on range transformations performed in three different RVC-packed reactors 50-mmol scale. Redox-neutral, oxidative, reductive processes were successfully implemented using suggested applicable frequency ranges further investigated types reactions. The advantages AC-enabled - such absence stirring maximized surface area electrodes provide possibility its universal application both small-scale screening experimentation large-scale preparative electrosynthesis without significant optimization needed between.

Язык: Английский

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Revisiting alternating current electrolysis for organic synthesis

Current Opinion in Electrochemistry, Год журнала: 2023, Номер 43, С. 101439 - 101439

Опубликована: Дек. 27, 2023

Язык: Английский

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Electrochemical dual α,β-C(sp³)–H functionalization of cyclic N-aryl amines

Green Chemistry, Год журнала: 2023, Номер 25(7), С. 2681 - 2689

Опубликована: Янв. 1, 2023

Herein, a straightforward route for dual α,β-C(sp 3 )–H functionalized cyclic N -aryl amines using combination of electrocatalysis and iron catalysis is disclosed, setting the stage challenging multiple site selective C–H functionalization.

Язык: Английский

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Intricacies of Mass Transport during Electrocatalysis: A Journey through Iron Porphyrin-Catalyzed Oxygen Reduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(22), С. 15619 - 15626

Опубликована: Май 23, 2024

Electrochemical steps are increasingly attractive for green chemistry. Understanding reactions at the electrode–solution interface, governed by kinetics and mass transport, is crucial. Traditional insights into these mechanisms limited, but our study bridges this gap through an integrated approach combining voltammetry, electrochemical impedance spectroscopy, electrospray ionization spectrometry. This technique offers real-time monitoring of chemical processes tracking changes in intermediates products during reactions. Applied to reduction oxygen catalyzed iron(II) tetraphenyl porphyrin complex, it successfully reveals various reaction degradation pathways under different kinetic regimes. Our findings illuminate complex electrocatalytic propose new ways studying alternating current voltage-pulse electrosynthesis. advancement enhances capacity optimize more sustainable processes.

Язык: Английский

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Machine learning-guided yield optimization for palladaelectro-catalyzed annulation reaction

Chem, Год журнала: 2024, Номер 10(7), С. 2283 - 2294

Опубликована: Июль 1, 2024

Electrosynthesis has become an increasingly popular platform in modern organic chemistry, possessing distinctive features and reaction parameters like applied current/potential, electrodes, electrolyte systems, cell design. While these unique give chemists more opportunities to control reactivity selectivity, they also increase the dimensionalities of a complicate interactions between variables, making optimization challenging. Herein, we present machine learning (ML) workflow that leverages physical descriptor-based yield prediction orthogonal experimental design strike delicate balance need for sampling diversity pursuit improvements, thereby efficiently identifying ideal conditions enantioselective palladaelectro-catalyzed annulation from extensive synthetic space. This work shows potential synergizing electrochemistry data-driven approach tackle multidimensional chemical problems.

Язык: Английский

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A machine learning strategy for enhancing the strength and toughness in metal matrix composites

International Journal of Mechanical Sciences, Год журнала: 2024, Номер 281, С. 109550 - 109550

Опубликована: Июль 8, 2024

Язык: Английский

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