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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A Survival Guide for the “Electro-curious”

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 53(1), P. 72 - 83

Published: Dec. 11, 2019

ConspectusThe appeal and promise of synthetic organic electrochemistry have been appreciated over the past century. In terms redox chemistry, which is frequently encountered when forging new bonds, it difficult to conceive a more economical way add or remove electrons than electrochemistry. Indeed, many largest industrial chemical processes are achieved in practical using as reagent. Why then, after so years documented benefits electrochemistry, not widely embraced by mainstream practitioners? Erroneous perceptions that "black box" combined with lack intuitive inexpensive standardized equipment likely contributed this stagnation interest within community. This barrier entry magnified fact can already be accomplished simple reagents even if they less atom-economic. Time has proven sustainability economics strong enough driving forces for adoption electrochemical techniques broader like chemists dabbled age-old technique, our first foray into area was choice but rather through sheer necessity.The unique reactivity old redox-modulating technique must therefore highlighted leveraged order draw field. Enabling bonds forged higher levels chemo- regioselectivity will accomplish goal. doing so, envisioned widespread go beyond supplanting unsustainable mundane reactions development exciting paradigms enable heretofore unimagined retrosynthetic pathways. Whereas rigorous physical principles electroorganic synthesis reviewed elsewhere, often case such summaries leave out pragmatic aspects designing, optimizing, scaling up preparative reactions. Taken together, task setting an reaction, much inventing one, vexing seasoned chemists. Account features format focuses on addressing exact issue context own studies. The graphically rich presentation style pinpoints basic concepts, typical challenges, key insights those "electro-curious" who seek rapidly explore power their research.

Language: Английский

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A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms

Chemical Science, Journal Year: 2019, Volume and Issue: 10(26), P. 6404 - 6422

Published: Jan. 1, 2019

A range of electroanalytical tools can be applied to studying redox reactions, probing key mechanistic questions in synthetic chemistry.

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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Manganese-Catalyzed Oxidative Azidation of C(sp³)–H Bonds under Electrophotocatalytic Conditions

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(41), P. 17693 - 17702

Published: Sept. 17, 2020

The selective installation of azide groups into C(sp3)-H bonds is a priority research topic in organic synthesis, particularly pharmaceutical discovery and late-stage diversification. Herein, we demonstrate generalized manganese-catalyzed oxidative azidation methodology using nucleophilic NaN3 as an source under electrophotocatalytic conditions. This approach allows us to perform the reaction without necessity adding excess substrate successfully avoiding use stoichiometric chemical oxidants such iodine(III) reagent or NFSI. A series tertiary secondary benzylic C(sp3)-H, aliphatic drug-molecule-based substrates are well tolerated our protocol. simultaneous gram-scale synthesis ease transformation amine collectively advocate for potential application preparative synthesis. Good reactivity bond selectivity incorporate nitrogen-based functionality at alkyl group also provide opportunities manipulate numerous medicinal candidates. We anticipate synthetic protocol, consisting metal catalysis, electrochemistry, photochemistry, would new sustainable option execute challenging transformations.

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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Nickel‐Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(15), P. 5033 - 5037

Published: Feb. 8, 2019

Transition-metal-catalyzed coupling reactions are useful tools for synthesizing aryl sulfur compounds. However, conventional transition-metal-catalyzed thiolation of bromides and chlorides typically requires the use strong base under elevated reaction temperature. Herein, we report first examples nickel-catalyzed electrochemical in absence an external at room temperature using undivided cells.

Language: Английский

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