Counter Electrode Reactions—Important Stumbling Blocks on the Way to a Working Electro‐organic Synthesis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(47)

Опубликована: Июнь 7, 2022

Over the past two decades, electro-organic synthesis has gained significant interest, both in technical and academic research as well terms of applications. The omission stoichiometric oxidizers or reducing agents enables a more sustainable route for redox reactions organic chemistry. Even if it is well-known that every electrochemical oxidation only viable with an associated reduction reaction vice versa, relevance counter often less addressed. In this Review, importance corresponding highlighted how can affect performance selectivity electrolytic conversion. A selection common strategies unique concepts to tackle issue are surveyed provide guide select appropriate synthesis.

Язык: Английский

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Electrochemical hydrogenation and oxidation of organic species involving water

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(4), С. 277 - 293

Опубликована: Март 25, 2024

Язык: Английский

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Versatile Tools for Understanding Electrosynthetic Mechanisms

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3292 - 3335

Опубликована: Дек. 17, 2021

Electrosynthesis is a popular, green alternative to traditional organic methods. Understanding the mechanisms not trivial yet necessary optimize reaction processes. To this end, multitude of analytical tools available identify and quantitate products intermediates. The first portion review serves as guide that underscores electrosynthesis fundamentals, including instrumentation, electrode selection, impacts electrolyte solvent, cell configuration, methods electrosynthesis. Next, broad base techniques aid in mechanism elucidation are covered detail. These divided into electrochemical, spectroscopic, chromatographic, microscopic, computational. Technique selection dependent on predicted pathways electrogenerated Often, combination must be utilized ensure accuracy proposed model. conclude, future prospects aim enhance field discussed.

Язык: Английский

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Catalysis for e-Chemistry: Need and Gaps for a Future De-Fossilized Chemical Production, with Focus on the Role of Complex (Direct) Syntheses by Electrocatalysis

ACS Catalysis, Год журнала: 2022, Номер 12(5), С. 2861 - 2876

Опубликована: Фев. 15, 2022

The prospects, needs and limits in current approaches catalysis to accelerate the transition e-chemistry, where this term indicates a fossil fuel-free chemical production, are discussed. It is suggested that e-chemistry necessary element of transformation meet targets net zero emissions by year 2050 conversion from petrochemistry feasible. However, acceleration development catalytic technologies based on use renewable energy sources (indicated as reactive catalysis) necessary, evidencing these part system changes thus should be assessed perspective. it perceived studies area not properly addressing develop required for presenting series relevant aspects directions which research focused framework implement e-chemistry.

Язык: Английский

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Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

Advanced Science, Год журнала: 2022, Номер 10(1)

Опубликована: Ноя. 18, 2022

Electro-organic synthesis has attracted a lot of attention in pharmaceutical science, medicinal chemistry, and future industrial applications energy storage conversion. To date, there not been detailed review on electro-organic with the strategy heterogeneous catalysis. In this review, most recent advances synthesizing value-added chemicals by catalysis are summarized. An overview electrocatalytic oxidation reduction processes as well paired electrocatalysis is provided, anodic alcohols (monohydric polyhydric), aldehydes, amines discussed. This also provides in-depth insight into cathodic carboxylates, carbon dioxide, CC, C≡C, reductive coupling reactions. Moreover, electro-synthesis methods, including parallel paired, sequential divergent convergent electrolysis, Additionally, strategies developed to achieve high electrosynthesis efficiency associated challenges addressed. It believed that promising direction organic electrochemistry, offering numerous opportunities develop new reaction methods.

Язык: Английский

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Electrocatalytic hydrogenation of quinolines with water over a fluorine-modified cobalt catalyst

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Сен. 8, 2022

Abstract Room temperature and selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines using a safe clean hydrogen donor catalyzed by cost-effective materials is significant yet challenging because the difficult activation H 2 . Here, fluorine-modified cobalt catalyst synthesized via electroreduction Co(OH)F precursor that exhibits high activity for electrocatalytic O as source produce with up 99% selectivity 94% isolated yield under ambient conditions. Fluorine surface-sites are shown enhance adsorption promote water active atomic (H*) forming F − -K + (H O) 7 networks. A 1,4/2,3-addition pathway involving H* proposed through combining experimental theoretical results. Wide substrate scopes, scalable synthesis bioactive precursors, facile preparation deuterated analogues, paired 1,2,3,4-tetrahydroquinoline industrially important adiponitrile at low voltage highlight promising applications this methodology.

Язык: Английский

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Emerging Graphene Derivatives and Analogues for Efficient Energy Electrocatalysis

Advanced Functional Materials, Год журнала: 2022, Номер 32(42)

Опубликована: Июнь 14, 2022

Abstract The demand for highly efficient conversion and storage of renewable energy sources calls advanced electrocatalytic technologies. 2D graphene has long been investigated as a versatile material platform with flexible structure tunable surface properties the design electrocatalysts. In recent years, new types derivatives analogues keep emerging showing great potential active selective applications. this review, progresses on electrocatalysis are summarized. This review starts from introduction requirements advantages analogues. Then advances introduced, including twisted superlattices, molecular‐level single‐atom catalysts, graphene‐supported dual‐atom catalysts or atomic clusters. next section deals research directions electrocatalysis, metal‐free materials, metallenes, transition metal borides (MBenes), strategies them. Finally, an overview development status field is provided, perspectives future technologies based materials proposed.

Язык: Английский

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Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26774 - 26782

Опубликована: Ноя. 29, 2023

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis alkenes all substitution patterns has been accomplished by means Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl as limiting reagents and exhibit a broad scope respect to both coupling partners. Notably, simple primary could be readily engaged carbon-centered radical precursors in reaction. This new protocol successfully demonstrated direct modification naturally occurring complex is amenable enantioselective arylacetic acid. Mechanistic studies, including series controlled experiments cyclic voltammetry data, allow us probe key intermediates pathway

Язык: Английский

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Paired Electrolysis Enabled Trifluoromethylheteroaromatization of Alkenes and Alkyne with Trifluoromethyl Thianthrenium Triflate (TT-CF₃⁺OTf^–) as a Bifunctional Reagent

Organic Letters, Год журнала: 2023, Номер 26(1), С. 411 - 415

Опубликована: Дек. 26, 2023

We report a strategic exploitation of trifluoromethyl thianthrenium triflate (TT-CF3+OTf–) as both electromediator and CF3 radical precursors for paired electrolysis. Enabled by this strategy, the three-component trifluoromethylheteroaromatization alkenes alkynes was realized. The superiority TT-CF3+OTf– to other electrophilic reagents is attributed cathodic generation thianthrene (TT) mediator, which shifts heterogeneous oxidation interest homogeneous one.

Язык: Английский

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Paired Electrosynthesis at Interdigitated Microband Array Electrodes without Intentionally Added Electrolyte: C–C Coupling of Dicyanobenzenes with Methanol

The Journal of Physical Chemistry C, Год журнала: 2025, Номер 129(6), С. 3014 - 3021

Опубликована: Фев. 3, 2025

The formation of substituted benzyl alcohols from dicyanobenzenes and methanol (C–C coupling) is demonstrated as a model system for paired electrosynthesis investigated at interdigitated microband array electrodes in microreactor with/without intentionally added supporting electrolyte. A Pt–Pt with 5 μm bands separated by gaps employed dimethyl sulfoxide (DMSO) solvent. Yields are optimized to approximately 50% the point 100% conversion. mechanism employing isotope labeling (CD3OD, CH3OD, d6-DMSO, 13CH3OH). methylene group (12C or 13C) obtained H2, D2, DH substitution patterns, hypothesis corresponding discussed aided density functional theory (DFT) calculations. Implications sustainable discussed.

Язык: Английский

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