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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Catalyzing Electrosynthesis: A Homogeneous Electrocatalytic Approach to Reaction Discovery

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 53(3), P. 547 - 560

Published: Feb. 20, 2020

Electrochemistry has been used as a tool to drive chemical reactions for over two centuries. With the help of an electrode and power source, chemists are bestowed with imaginary reagent whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds (e.g., F

Language: Английский

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New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(8), P. 1317 - 1340

Published: July 16, 2020

As the breadth of radical chemistry grows, new means to promote and regulate single-electron redox activities play increasingly important roles in driving modern synthetic innovation. In this regard, photochemistry electrochemistry-both considered as niche fields for decades-have seen an explosive renewal interest recent years gradually have become a cornerstone organic chemistry. Outlook article, we examine current state-of-the-art areas electrochemistry photochemistry, well nascent area electrophotochemistry. These techniques employ external stimuli activate molecules imbue privileged control reaction progress selectivity that is challenging traditional chemical methods. Thus, they provide alternative entries known reactive intermediates enable distinct strategies were previously unimaginable. Of many hallmarks, electro- are often classified "green" technologies, promoting reactions under mild conditions without necessity potent wasteful oxidants reductants. This reviews most growth these with special emphasis on conceptual advances given rise enhanced accessibility tools trade.

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 electrochemical oxidative cross-coupling with hydrogen evolution involving radicals

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(18), P. 10058 - 10086

Published: Jan. 1, 2021

This tutorial review provides an overview of the most recent developments in electrochemical oxidative cross-coupling with hydrogen evolution involving radicals.

Language: Английский

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Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(49), P. 20661 - 20670

Published: Nov. 24, 2020

Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated variety of alkene functionalization reactions, most which proceed via an anodic oxidation pathway. In this report, we further expand the scope electrochemistry reductive alkenes. particular, strategic choice reagents reaction conditions enabled radical-polar crossover pathway wherein two distinct electrophiles can be added across highly chemo- regioselective fashion. Specifically, used strategy intermolecular carboformylation, anti-Markovnikov hydroalkylation, carbocarboxylation alkenes—reactions with rare precedents literature—by means electroreductive generation alkyl radical carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) simple, transition-metal-free display broad substrate good tolerance functional groups. A uniform protocol achieve all three transformations by simply altering medium. development provides new avenue for constructing Csp3–Csp3 bonds.

Language: Английский

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New Bisoxazoline Ligands Enable Enantioselective Electrocatalytic Cyanofunctionalization of Vinylarenes

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(37), P. 14480 - 14485

Published: Sept. 9, 2019

In contrast to the rapid growth of synthetic electrochemistry in recent years, enantioselective catalytic methods powered by electricity remain rare. this work, we report development a highly method for electrochemical cyanophosphinoylation vinylarenes. A new family serine-derived chiral bisoxazolines with ancillary coordination sites were identified as optimal ligands.

Language: Английский

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3d metallaelectrocatalysis for resource economical syntheses

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(13), P. 4254 - 4272

Published: Jan. 1, 2020

This review summarizes key developments in 3d metallaelectrocatalysis the context of resource economy molecular syntheses.

Language: Английский

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Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Science, Journal Year: 2021, Volume and Issue: 371(6528), P. 507 - 514

Published: Jan. 28, 2021

Vicinal dibromides and dichlorides are important commodity chemicals indispensable synthetic intermediates in modern chemistry that traditionally synthesized using hazardous elemental chlorine bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for facile scalable interconversion alkenes vicinal dihalides, a class reactions can be used both synthesize useful dihalogenated molecules from simple recycle waste material through retro-dihalogenation. The reaction is demonstrated 1,2-dibromoethane, as well 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, dibrominate dichlorinate, respectively, wide range setup with inexpensive graphite electrodes. Conversely, hexachlorinated persistent pollutant lindane could fully dechlorinated benzene soil samples alkene acceptors.

Language: Английский

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Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(2), P. 165 - 178

Published: March 29, 2021

There is a resurgence of interests in organic electrochemistry, which generally accepted as green synthetic tool. In this context, many electrochemical methods have been developed the past decade to access various nitrogen-centered radicals (NCRs) from readily available precursors controlled fashion, enabling rapid development NCR-mediated new reactions for construction nitrogen-containing compounds. review, recent advances chemistry electrochemically generated NCRs are critically highlighted, based on strategies their formation and types NCRs. Focus put mechanism generation different applications.

Language: Английский

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