Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 7941 - 8002

Published: Jan. 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.

Language: Английский

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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

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Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts

Science Bulletin, Journal Year: 2021, Volume and Issue: 66(23), P. 2412 - 2429

Published: July 13, 2021

Language: Английский

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Emerging chemistries and molecular designs for flow batteries

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(8), P. 524 - 543

Published: June 17, 2022

Language: Английский

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Green Chemistry: Electrochemical Organic Transformations via Paired Electrolysis

ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(18), P. 6148 - 6169

Published: April 27, 2021

Paired electrolysis is highly valuable from the viewpoint of efficiency as well atom and energy economies. In order to optimize latter two for chemical reactions, development paired electrochemical processes necessary. When both electrodes in an cell (divided undivided) are applied working electrodes, sides (oxidation reduction) yield compounds, this ideal phenomena defined electrosynthesis. This offers opportunity reduce spent time, when compared with a single system that only used achieve product interest, while ignoring other side (anodic or cathodic). case, 200% current could be achieved during electrosynthesis using cathodic anodic provide same product. efficient green process and, therefore, beneficial preserving resources minimizing waste. However, beneficial, oxidation reduction must compatible counter losses equally ease separation purification electrode products. Greater efforts required perform more systematic rational approach optimal products under conditions. Nevertheless, new computational tools assistance matter. There considerable level adventure designing electrosynthetic accompanying opportunities design innovative powerful synthetic strategies. Herein, overview several examples electrosyntheses their advantages summarized will aid researchers develop greater understanding subject subsequently employ sustainable synthesis organic molecules.

Language: Английский

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Nickel/biimidazole-catalyzed electrochemical enantioselective reductive cross-coupling of aryl aziridines with aryl iodides

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 22, 2023

Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with iodides in undivided cell, affording β-phenethylamines good to excellent enantioselectivity broad functional group tolerance. The combination cyclic voltammetry analysis the catalyst reduction potential as well electrode study provides a convenient route for reaction optimization. Overall, high efficiency this method is credited electroreduction-mediated turnover nickel instead metal reductant-mediated turnover. Mechanistic studies suggest radical pathway involved ring opening aziridines. statistical serves compare different design requirements photochemically and electrochemically mediated reactions under type mechanistic manifold.

Language: Английский

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Enantioselective Reductive Cross-Couplings of Olefins by Merging Electrochemistry with Nickel Catalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 23910 - 23917

Published: Oct. 26, 2023

The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development electroreductive cross-couplings olefins remains challenge. Inspired by advantages synergistic use with nickel catalysis, we present here Ni-catalyzed cross-coupling acrylates aryl halides alkyl bromides, which affords chiral α-aryl carbonyls good excellent enantioselectivity. Additionally, this catalytic reaction can be applied (hetero)aryl chlorides, is difficult achieve other methods. combination cyclic voltammetry analysis electrode potential studies suggests that NiI species activates oxidative addition bromides single-electron transfer.

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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Transition metal-catalyzed organic reactions in undivided electrochemical cells

Chemical Science, Journal Year: 2021, Volume and Issue: 12(39), P. 12866 - 12873

Published: Jan. 1, 2021

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts alter selectivity given transformation.

Language: Английский

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Nickel‐Catalyzed N‐Arylation of NH‐Sulfoximines with Aryl Halides via Paired Electrolysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(17), P. 9444 - 9449

Published: Feb. 12, 2021

Abstract A novel strategy for the N‐arylation of NH‐sulfoximines has been developed by merging nickel catalysis and electrochemistry (in an undivided cell), thereby providing a practical method construction sulfoximine derivatives. Paired electrolysis is employed in this protocol, so sacrificial anode not required. Owing to mild reaction conditions, excellent functional group tolerance yield are achieved. preliminary mechanistic study indicates that anodic oxidation Ni II species crucial promote reductive elimination C−N bond from resulting III at room temperature.

Language: Английский

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