Electrochemical strategies for C–H functionalization and C–N bond formation

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(15), P. 5786 - 5865

Published: Jan. 1, 2018

This review provides an overview of the use electrochemistry as appealing platform for expediting carbon–hydrogen functionalization and carbon–nitrogen bond formation.

Language: Английский

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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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The Persistent Radical Effect in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(1), P. 74 - 108

Published: May 22, 2019

Abstract Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if have lifetimes they generated at equal rates, will become dominant process. This high cross‐selectivity based on kinetic phenomenon called persistent radical effect (PRE). In this Review, an explanation PRE supported by simulations simple model systems provided. Radical stabilities discussed within context their lifetimes, various examples PRE‐mediated radical–radical in synthesis summarized. It shown that restricted to coupling with transient radical. If one partner longer‐lived than other radical, operates achieved. important point expands scope chemistry. The Review divided into parts, namely 1) or organic 2) “radical–metal crossover reactions”; here, metal‐centered species more generally transition‐metal complexes able react discussed—a field has flourished recently.

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

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(3), P. 3180 - 3218

Published: Nov. 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.

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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Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes

Nature Chemistry, Journal Year: 2020, Volume and Issue: 12(8), P. 747 - 754

Published: June 29, 2020

Language: Английский

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Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C–H/N–H Activation with Internal Alkynes

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(25), P. 7913 - 7921

Published: May 29, 2018

Electrochemical oxidative C–H/N–H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations internal alkynes. The electro-oxidative C–H activation manifold proved viable an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant catalysts. electrochemical catalysis prevents the use transition metal oxidants catalysis, generating H2 as sole byproduct. Detailed mechanistic studies provided strong support for facile cobaltation by initially formed cobalt(III) catalyst. subsequent alkyne migratory insertion was interrogated mass spectrometry and DFT calculations, providing formation key seven-membered cobalta(III) cycle regioselective fashion. Key to success unprecedented alkynes represented N-2-pyridylhydrazides, which we developed traceless electrocleavage strategy electroreductive samarium temperature.

Language: Английский

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