Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Год журнала: 2021, Номер 50(14), С. 7941 - 8002

Опубликована: Янв. 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.

Язык: Английский

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Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Год журнала: 2021, Номер 7(3), С. 415 - 431

Опубликована: Март 9, 2021

Efficient and selective molecular syntheses are paramount to

Язык: Английский

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Electro-organic synthesis – a 21^stcentury technique

Chemical Science, Год журнала: 2020, Номер 11(46), С. 12386 - 12400

Опубликована: Янв. 1, 2020

This perspective provides insight into recent electro-organic methods and general trends in this field, opens up prospects for future viewpoints.

Язык: Английский

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Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(36), С. 19572 - 19590

Опубликована: Фев. 19, 2021

Abstract Compared to modern fossil‐fuel‐based refineries, the emerging electrocatalytic refinery (e‐refinery) is a more sustainable and environmentally benign strategy convert renewable feedstocks energy sources into transportable fuels value‐added chemicals. A crucial step in conducting e‐refinery processes development of appropriate reactions optimal electrocatalysts for efficient cleavage formation chemical bonds. However, compared well‐studied primary (e.g., O 2 reduction, water splitting), mechanistic aspects materials design complex are yet be settled. To address this challenge, herein, we first present fundamentals heterogeneous electrocatalysis some reactions, then implement these establish framework by coupling situ generated intermediates (integrated reactions) or products (tandem reactions). We also set principles strategies efficiently manipulate reaction pathways.

Язык: Английский

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

Chem, Год журнала: 2020, Номер 6(10), С. 2484 - 2496

Опубликована: Сен. 24, 2020

Язык: Английский

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

ACS Central Science, Год журнала: 2020, Номер 6(8), С. 1317 - 1340

Опубликована: Июль 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.

Язык: Английский

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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2487 - 2649

Опубликована: Ноя. 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.

Язык: Английский

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Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3180 - 3218

Опубликована: Ноя. 19, 2021

Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis been popular improving selectivity and efficiency a wide variety of energy-related applications, last two decades, there much interest to develop conceptually novel transformations, selective functionalization, sustainable reactions. This review discusses recent advances combination electrochemistry homogeneous transition-metal catalysis synthesis. The enabling mechanistic studies are presented alongside advantages as well future directions address challenges metal-catalyzed electrosynthesis.

Язык: Английский

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Radical philicity and its role in selective organic transformations

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(7), С. 486 - 499

Опубликована: Июнь 22, 2021

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(41), С. 17693 - 17702

Опубликована: Сен. 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.

Язык: Английский

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