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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Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 415 - 431

Published: March 9, 2021

Efficient and selective molecular syntheses are paramount to

Language: Английский

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Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

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Powering the Future: How Can Electrochemistry Make a Difference in Organic Synthesis?

Chem, Journal Year: 2020, Volume and Issue: 6(10), P. 2484 - 2496

Published: Sept. 24, 2020

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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Synthetic Photoelectrochemistry

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(29), P. 11732 - 11747

Published: Dec. 5, 2019

Photoredox catalysis (PRC) and synthetic organic electrochemistry (SOE) are often considered competing technologies in synthesis. Their fusion has been largely overlooked. We review state-of-the-art photoelectrochemistry, grouping examples into three categories: 1) electrochemically mediated photoredox (e-PRC), 2) decoupled photoelectrochemistry (dPEC), 3) interfacial (iPEC). Such synergies prove beneficial not only for "greenness" chemical selectivity, but also the accumulation of energy accessing super-oxidizing or -reducing single electron transfer (SET) agents. Opportunities challenges this emerging exciting field discussed.

Language: Английский

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Recent advances in visible light-activated radical coupling reactions triggered by (i) ruthenium, (ii) iridium and (iii) organic photoredox agents

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(17), P. 9540 - 9685

Published: Jan. 1, 2021

Visible light-activated reactions continue to expand and diversify. The example shown here is a Birch reduction achieved by organophotoredox reagents.

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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Scalable Photoelectrochemical Dehydrogenative Cross‐Coupling of Heteroarenes with Aliphatic C−H Bonds

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(34), P. 14275 - 14280

Published: June 3, 2020

Heteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative cross-coupling of heteroarenes with aliphatic C-H bonds provides straightforward access to functionalized from readily available Established methods employ stoichiometric chemical oxidants under conditions heating or light irradiation. By merging electrochemistry photochemistry, we have achieved efficient photoelectrochemical dehydrogenative C(sp3 )-H donors through H2 evolution, without the addition metal catalysts oxidants. Mechanistically, donor is converted a nucleophilic carbon radical H-atom transfer chlorine atom, which produced by irradiation anodically generated Cl2 Cl- . The then undergoes substitution heteroarene afford alkylated products.

Language: Английский

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