Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Год журнала: 2021, Номер 50(14), С. 7941 - 8002

Опубликована: Янв. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Язык: Английский

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Reproducibility in Electroorganic Synthesis—Myths and Misunderstandings

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(27), С. 14750 - 14759

Опубликована: Янв. 15, 2021

The use of electric current as a traceless activator and reagent is experiencing renaissance. This sustainable synthetic method evolving into hot topic in contemporary organic chemistry. Since researchers with various scientific backgrounds are entering this interdisciplinary field, different parameters methods reported to describe the experiments. variation can lead problems reproducibility electroorganic syntheses. As an example, such density or electrode distance some cases more significant than often anticipated. Minireview provides guidelines on reporting electrosynthetic data dispels myths about technique, thereby streamlining experimental facilitate reproducibility.

Язык: Английский

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The E factor at 30: a passion for pollution prevention

Green Chemistry, Год журнала: 2023, Номер 25(5), С. 1704 - 1728

Опубликована: Янв. 1, 2023

Publication of the E Factor drew attention to problem waste in chemicals manufacture. Thirty yeas later it is abundantly clear that underlying cause global environmental problems, from climate change plastic pollution.

Язык: Английский

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Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

eScience, Год журнала: 2022, Номер 2(3), С. 243 - 277

Опубликована: Апрель 23, 2022

Compared with general redox chemistry, electrochemistry using the electron as a potent, controllable, yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis. With its environmentally benign features gradually being uncovered and studied, electrosynthesis is currently undergoing revival becoming rapidly growing area within synthetic community. Among electrochemical transformations, anodically enabled ones have been far extensively exploited than those driven by cathodic reduction, although both approaches are conceptually attractive. To stimulate development of cathodically reactions, this review summarizes recently developed reductive electrosynthetic protocols, discussing highlighting reaction features, substrate scopes, applications, plausible mechanisms reveal recent trends in area. Herein, reduction-enabled preparative transformations categorized into four types: reduction (1) unsaturated hydrocarbons, (2) heteroatom-containing carbon-based systems, (3) saturated C-hetero or C–C polar/strained bonds, (4) hetero-hetero linkages. Apart from net electroreductive few examples photo-electrosynthesis well paired electrolysis also introduced, which offer opportunities overcome certain limitations improve versatility. The electrochemically driven, transition metal-catalyzed cross-couplings that comprehensively discussed several other reviews not included here.

Язык: Английский

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Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 121(17), С. 10241 - 10270

Опубликована: Июль 6, 2021

The critical aspects of the corrosion metal electrodes in cathodic reductions are covered. We discuss involved mechanisms including alloying with alkali metals, etching aqueous and aprotic media, formation hydrides organometallics. Successful approaches that have been implemented to suppress reviewed. present several examples from electroorganic synthesis where clever use alloys instead soft neat heavy metals application protective cationic additives allowed successfully exploit these materials as cathodes. Because high overpotential for hydrogen evolution reaction, such cathodes can contribute toward more sustainable green synthetic processes. reported strategies expand applications organic electrosynthesis because a negative regime is accessible within protic media common poisons, e.g., sulfur-containing substrates, compatible strongly diminished side reaction paves way efficient reductive conversions.

Язык: Английский

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Unlocking the Potential of High-Throughput Experimentation for Electrochemistry with a Standardized Microscale Reactor

ACS Central Science, Год журнала: 2021, Номер 7(8), С. 1347 - 1355

Опубликована: Авг. 5, 2021

Organic electrochemistry has emerged as an enabling and sustainable technology in modern organic synthesis. Despite the recent renaissance of electrosynthesis, broad adoption synthetic community, especially industrial settings, been hindered by lack general, standardized platforms for high-throughput experimentation (HTE). Herein, we disclose design HT

Язык: Английский

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Interfacing single-atom catalysis with continuous-flow organic electrosynthesis

Chemical Society Reviews, Год журнала: 2022, Номер 51(10), С. 3898 - 3925

Опубликована: Янв. 1, 2022

This manuscript reviews for the first time developments at interface between organic electrosynthesis and single-atom catalysis, highlighting advantages in shifting from a batch to flow production.

Язык: Английский

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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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Electroreduction Enables Regioselective 1,2‐Diarylation of Alkenes with Two Electrophiles

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(17)

Опубликована: Фев. 24, 2023

Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of electrophiles is in crucial demand, yet challenging for cross-electrophile-coupling. Herein, we demonstrate redox-mediated electrolysis, which aryl nitriles are both radical precursors and redox-mediators, enables an intermolecular alkene 1,2-diarylation with remarkable regioselectivity, thereby avoiding involvement transition-metal catalysts. This transformation utilizes cyanoarene anions activating various halides (including iodides, bromides, even chlorides) affords adducts up 83 % yield >20 : 1 regioselectivity more than 80 examples, providing feasible approach bibenzyl derivatives.

Язык: Английский

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Paired Oxidative and Reductive Catalysis: Breaking the Potential Barrier of Electrochemical C(sp³)−H Alkenylation**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(24)

Опубликована: Апрель 1, 2023

Due to the intrinsic inertness of alkanes, strong oxidative conditions are typically required enable their C(sp3 )-H functionalization. Herein, a paired electrocatalysis strategy was developed by integrating catalysis with reductive in one cell without interference, which earth-abundant iron and nickel employed as anodic cathodic catalysts, respectively. This approach lowers previously high oxidation potential for alkane activation, enabling electrochemical functionalization at ultra-low ≈0.25 V vs. Ag/AgCl under mild conditions. Structurally diverse alkenes, including challenging all-carbon tetrasubstituted olefins, can be accessed using readily available alkenyl electrophiles.

Язык: Английский

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