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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Electrochemical Oxidation Induced Selective C–C Bond Cleavage

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 485 - 505

Published: Oct. 5, 2020

Selective C–C bond cleavage under mild conditions can serve as a valuable tool for organic syntheses and macromolecular degradation. However, the conventional chemical methods have largely involved use of noble transition-metal catalysts well stoichiometric perhaps environmentally unfriendly oxidants, compromising overall sustainable nature transformation chemistry. In this regard, electrochemical has been identified scalable strategy that employs electricity to replace byproduct-generating reagents. To date, progress made in area mainly relied on Kolbe electrolysis related processes. Encouragingly, more examples bonds via other maneuvers recently developed. This review provides an overview most recent significant developments electrochemically oxidative selective cleavage, with emphasis both synthetic outcomes reaction mechanisms, it showcases innate advantages exciting potentials synthesis.

Language: Английский

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Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

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Photocatalysis in the Life Science Industry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

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Visible‐Light‐Induced Homolysis of Earth‐Abundant Metal‐Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21100 - 21115

Published: Feb. 18, 2021

Abstract The mainstream applications of visible‐light photoredox catalysis predominately involve outer‐sphere single‐electron transfer (SET) or energy (EnT) processes precious metal Ru II Ir III complexes organic dyes with low photostability. Earth‐abundant metal‐based M n L ‐type (M=metal, =polydentate ligands) are rapidly evolving as alternative photocatalysts they offer not only economic and ecological advantages but also access to the complementary inner‐sphere mechanistic modes, thereby transcending their inherent limitations ultrashort excited‐state lifetimes for use effective photocatalysts. generic process, termed visible‐light‐induced homolysis (VLIH), entails formation suitable light‐absorbing ligated metal–substrate (M ‐Z; Z=substrate) that can undergo homolytic cleavage generate n−1 Z . further 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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