Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)
Published: April 22, 2024
Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrochemically mediated Atom Transfer Radical Polymerization (eATRP) facilitate the regeneration of activator Cu
Language: Английский
Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(2), P. 338 - 366
Published: Jan. 18, 2024
This review summarizes examples of organic electrosynthesis from the peer-reviewed literature 2000 to 2023 that have been conducted on scales 20 g or above. A significant portion these were a ≤100 scale, while detailed reports kilogram-scale remain scarce in pharmaceutical industry. In addition chemical transformation, this also highlights type reactor used and projected productivity metric as ways compare different reports. The selected scale-ups described herein illustrate remaining challenges currently preventing routine use large-scale
Language: Английский
Citations
42
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: July 23, 2024
Abstract It is vital to explore effective ways for prolonging electrode lifespans under harsh electrolysis conditions, such as high current densities, acid environment, and impure water source. Here we report alternating approaches that realize promptly regularly repair/maintenance concurrent bubble evolution. Electrode are improved by co-action of Fe group elemental ions alkali metal cations, especially a unique Co 2+ -Na + combo. A commercial Ni foam sustains ampere-level densities alternatingly during continuous 93.8 h in an acidic solution, whereas completely dissolved ~2 conventional conditions. The work not only explores electrolysis-based system, cation-based catalytic systems, electrodeposition techniques, beyond, but demonstrates the possibility prolonged repeated deposition-dissolution processes. With enough adjustable experimental variables, upper improvement limit lifespan would be high.
Language: Английский
Citations
36
Science, Journal Year: 2024, Volume and Issue: 385(6705), P. 216 - 223
Published: July 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.
Language: Английский
Citations
27
Current Opinion in Electrochemistry, Journal Year: 2024, Volume and Issue: 44, P. 101441 - 101441
Published: Jan. 11, 2024
The field of organic electrochemistry has regained significant interest over recent years. unique level control afforded to the user reaction kinetics and selectivity is a driving force behind this. use non-standard electrolysis waveforms, such as alternating polarity electrolysis, been shown offer degree variation that facilitates new opportunities in field. generation pulsed waveforms via introduction resting period during underexplored electrosynthesis. Recent case studies demonstrate this potentially powerful technique can aid dynamic redox environments for greater success.
Language: Английский
Citations
12
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)
Published: March 20, 2024
Olefin hydrogenation is one of the most important transformations in organic synthesis. Electrochemical transition metal-catalyzed an attractive approach to replace dangerous hydrogen gas with electrons and protons. However, this reaction poses major challenges due rapid evolution (HER) metal-hydride species that outcompetes alkene step, facile deposition metal catalyst at electrode stalls reaction. Here we report economical efficient strategy achieve high selectivity for reactivity over well-established HER. Using inexpensive bench-stable nickel salt as catalyst, mild features outstanding substrate generality functional group compatibility, distinct chemoselectivity. In addition, hydrodebromination alkyl aryl bromides could be realized using same system a different ligand, chemoselectivity between achieved through ligand selection. The practicability our method has been demonstrated by success large-scale synthesis catalytic amount electrolyte minimal solvent. Cyclic voltammetry kinetic studies were performed, which support Ni
Language: Английский
Citations
10
Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(5), P. 1877 - 1885
Published: March 1, 2024
The burgeoning interest in new electrochemical methods holds promise to provide a plethora of strategic disconnections for pharmaceutical compounds that are safer, less wasteful, and more streamlined than traditional chemical strategies. use organic electrochemistry the commercial production pharmaceuticals is exceedingly rare due lack modular infrastructure. Herein we describe cascading continuous stirred tank reactors with individual cell potential control applied over reaction "stages" which demonstrate balance between high selectivity throughput necessary be viable strategy space. Using degree afforded by this reactor design, 1 kg demonstration was achieved 9 h yield (2.6 kg/day throughput).
Language: Английский
Citations
8
Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.
Language: Английский
Citations
1
Current Opinion in Electrochemistry, Journal Year: 2023, Volume and Issue: 43, P. 101439 - 101439
Published: Dec. 27, 2023
Language: Английский
Citations
17
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15619 - 15626
Published: May 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.
Language: Английский
Citations
7
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)
Published: Oct. 31, 2023
The difunctionalization of alkenes-a process that installs two functional groups in a single operation and transforms chemical feedstocks into value-added products-is one the most appealing synthetic methods contemporary chemistry. However, introduction distinct via readily accessible nucleophiles remains formidable challenge. Existing intermolecular alkene azidocyanation methods, which primarily focus on aryl alkenes rely stoichiometric oxidants. We report herein an unprecedented electrochemical strategy for is compatible with both alkyl alkenes. This achieved by harnessing finely-tuned anodic electron transfer strategic selection copper/ligand complexes. reactions were rendered enantioselective employing chiral ligand. Crucially, mild conditions well-regulated assure exceptional tolerance various substrate compatibility terminal internal
Language: Английский
Citations
15