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

eScience, Journal Year: 2022, Volume and Issue: 2(3), P. 243 - 277

Published: April 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.

Language: Английский

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Metal‐Free Electrochemical Carboxylation of Organic Halides in the Presence of Catalytic Amounts of an Organomediator

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 26, 2022

Herein, an electroreductive carboxylation of organic carbon-halogen bonds (X=Br and Cl) promoted by catalytic amounts naphthalene as mediator is reported. This transformation proceeds smoothly under mild conditions with a broad substrate scope 59 examples, affording the valuable versatile carboxylic acids in moderate to excellent yields without need costly transition metal, wasted stoichiometric metal reductants, or sacrificial anodes. Further late-stage carboxylations natural product drug derivatives demonstrate its synthetic utility. Mechanistic studies confirmed activation via single-electron transfer key role this reaction.

Language: Английский

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Asymmetric-waveform alternating current-promoted silver catalysis for C–H phosphorylation

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(2), P. 172 - 181

Published: Jan. 5, 2023

Language: Английский

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Electrochemical radical-polar crossover: a radical approach to polar chemistry

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 450 - 470

Published: Nov. 3, 2023

Language: Английский

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Recent Advances in Asymmetric Organometallic Electrochemical Synthesis (AOES)

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 19, 2025

ConspectusIn recent years, our research group has dedicated significant effort to the field of asymmetric organometallic electrochemical synthesis (AOES), which integrates electrochemistry with transition metal catalysis. On one hand, we have rationalized that compounds can serve as molecular electrocatalysts (mediators) reduce overpotentials and enhance both reactivity selectivity reactions. other conditions for catalysis be substantially improved through electrochemistry, enabling precise modulation metal's oxidation state by controlling potentials regulating electron transfer rate via current adjustments. This synergistic approach addresses key challenges inherent in traditional catalysis, particularly those related use redox-active chemical reagents. Furthermore, redox conveniently tuned modifying their ligands, thereby governing reaction regioselectivity stereoselectivity. As a result, AOES emerged powerful promising tool chiral compounds.In this Account, summarize contextualize efforts AOES. Our primary strategy involves leveraging controllability potential regulate organometallics, facilitating desired An efficient platform was established under mild conditions, significantly reducing reliance on been systematically categorized into three sections based distinct electrolysis modes: combined anodic oxidation, cathodic reduction, paired electrolysis. In each section, highlight innovative discoveries tailored unique characteristics respective modes.In many transformations, metal-catalyzed reactions involving reagents utilizing exhibit similar reactivities. However, also observed notable differences certain cases. These findings include following: (1) Enhanced efficiency synthesis: instance, Rh-catalyzed enantioselective functionalization C–H bonds demonstrates superior efficiency. (2) Expanded scope transformations: previously challenging achieved due tunability potentials. A example is reductive coupling aryl chlorides, expands range accessible transformations. Additionally, mechanistic studies explore techniques intrinsic such controlled experiments, impact electrode materials catalyst performance, cyclic voltammetry studies. investigations provide more intuitive understanding behavior catalysts study mechanisms, guide design new catalytic systems.The advancements offer robust environmentally friendly sustainable selective By integrating developed versatile organic not only enhances but reduces environmental impact. We anticipate Account will stimulate further innovation realm AOES, leading discovery systems development synthetic methodologies.

Language: Английский

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Zinc-free, Scalable Reductive Cross-Electrophile Coupling Driven by Electrochemistry in an Undivided Cell

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(20), P. 12617 - 12626

Published: Oct. 3, 2022

Nickel-catalyzed reductive cross-electrophile coupling reactions are becoming increasingly important in organic synthesis, but application at scale is limited by three interconnected challenges: a reliance on amide solvents (complicated workup, regulated), the generation of stoichiometric Zn salts isolation, waste disposal issue), and mixing/activation challenges zinc powder. We show here an electrochemical approach that addresses these issues: reaction works acetonitrile with diisopropylethylamine as terminal reductant simple undivided cell (graphite(+)/nickel foam(-)). The utilizes combination two ligands, 4,4'-di-

Language: Английский

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Electrophotocatalytic C−H Functionalization of N‐Heteroarenes with Unactivated Alkanes under External Oxidant‐Free Conditions

ChemSusChem, Journal Year: 2021, Volume and Issue: 15(6)

Published: Dec. 30, 2021

The Minisci alkylation of N-heteroarenes with unactivated alkanes under external oxidant-free conditions provides an economically attractive route to access alkylated but remains underdeveloped. Herein, a new electrophotocatalytic strategy alkyl radicals from strong C(sp3 )-H bonds was reported for the following reactions in absence chemical oxidants. This realized first example cerium-catalyzed reaction directly abundant excellent atom economy. It is anticipated that general design principle would enrich catalytic strategies explore functionalizations H2 evolution.

Language: Английский

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Electrocatalytic Oxidative Hydrofunctionalization Reactions of Alkenes via Co(II/III/IV) Cycle

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(4), P. 2132 - 2137

Published: Jan. 27, 2022

Here we disclose a general Co(II/III/IV) electrocatalytic platform for alkene functionalization. Driven by electricity, set of the oxidative hydrofunctionalization reactions via hydrogen atom transfer were demonstrated without need stochiometric chemical oxidants. The scope encompasses hydroalkoxylation, hydroacyloxylation, hydroarylation, semipinacol rearrangement, and deallylation. Mechanistic studies stereochemical evidence support an ECEC process involving electrochemically generated organocobalt(IV) intermediate. This work presents example reactivity space expansion in electrocatalysis VB12-system going beyond common oxidation states Co(I/II/III).

Language: Английский

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Comprehensive Comparisons between Directing and Alternating Current Electrolysis in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Aug. 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.

Language: Английский

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Electrochemical organic reactions: A tutorial review

Frontiers in Chemistry, Journal Year: 2023, Volume and Issue: 10

Published: Jan. 10, 2023

Although the core of electrochemistry involves simple oxidation and reduction reactions, it can be complicated in real electrochemical organic reactions. The principles used reactions have been derived using physical chemistry, which drives other organic/inorganic This review mainly comprises two themes: first discusses factors that help optimize an reaction, including electrodes, supporting electrolytes, cell design, second outlines studies conducted field over a period 10 years. Electrochemical as versatile tool for synthetically important by modifying constant electrolysis current.

Language: Английский

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