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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Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1875 - 1924

Published: Aug. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

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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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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Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis

Chem Catalysis, Journal Year: 2021, Volume and Issue: 1(3), P. 523 - 598

Published: May 24, 2021

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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Radical C(sp3)–H functionalization and cross-coupling reactions

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(6), P. 405 - 427

Published: May 17, 2022

Language: Английский

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Electrophotocatalysis: Combining Light and Electricity to Catalyze Reactions

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12567 - 12583

Published: July 11, 2022

Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions that have received tremendous attention in recent years. In contrast, processes combine these modalities, an area termed electrophotocatalysis, until recently remained quite rare. However, over past several years a number reports this shown potential combining power light electrical energy to realize new catalytic transformations. Electrophotocatalysis offers ability perform photoredox without need large quantities stoichiometric or superstoichiometric oxidants reductants by making use electrochemical as electron source sink. addition, electrophotocatalysis is readily amenable generation open-shell photocatalysts, which tend exceptionally strong redox potentials. way, potent yet selective been realized under relatively mild conditions. This Perspective highlights advances provides some possible avenues future work growing area.

Language: Английский

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Synthetic Molecular Photoelectrochemistry: New Frontiers in Synthetic Applications, Mechanistic Insights and Scalability

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(12)

Published: Sept. 3, 2021

Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single-electron transfer (SET) reactions in much greener way broadens redox window possible transformations. Herein, most recent contributions are reviewed, demonstrating exciting opportunities, namely, combination with other reactivity paradigms (hydrogen-atom transfer, radical polar crossover, energy sensitization), scalability up to multigram scale, novel selectivities SET super-oxidations/reductions importance precomplexation temporally enable excited ion catalysis.

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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