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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Metalla-electrocatalyzed C–H Activation by Earth-Abundant 3d Metals and Beyond

Accounts of Chemical Research, Год журнала: 2019, Номер 53(1), С. 84 - 104

Опубликована: Дек. 19, 2019

To improve the efficacy of molecular syntheses, researchers wish to capitalize upon selective modification otherwise inert C-H bonds. The past two decades have witnessed considerable advances in coordination chemistry that set stage for transformative tools functionalizations. Particularly, oxidative C-H/C-H and C-H/Het-H transformations gained major attention because they avoid all elements substrate prefunctionalization. Despite advances, activations been dominated by precious transition metal catalysts based on palladium, ruthenium, iridium, rhodium, thus compromising sustainable nature overall activation approach. same holds true predominant use stoichiometric chemical oxidants regeneration active catalyst, prominently featuring hypervalent iodine(III), copper(II), silver(I) oxidants. Thereby, quantities undesired byproducts are generated, which preventive applications scale. In contrast, elegant merger homogeneous metal-catalyzed with electrosynthesis bears unique power achieve outstanding levels oxidant resource economy. Thus, contrast classical electrosyntheses control, metalla-electrocatalysis huge largely untapped potential unmet site selectivities means catalyst control. While indirect electrolysis using palladium complexes has realized, less toxic expensive base feature distinct beneficial assets toward this Account, I summarize emergence electrocatalyzed earth-abundant 3d metals beyond, a topical focus contributions from our laboratories through November 2019. cobalt electrocatalysis was identified as particularly powerful platform wealth transformations, including oxygenations nitrogenations well alkynes, alkenes, allenes, isocyanides, carbon monoxide, among others. As complementary tools, nickel, copper, very recently iron devised metalla-electrocatalyzed activations. Key success were detailed mechanistic insights, oxidation-induced reductive elimination scenarios. Likewise, development methods make weak O-coordination benefited crucial insights into catalyst's modes action experiment, operando spectroscopy, computation. Overall, thereby syntheses These electrooxidative frequently characterized improved chemoselectivities. Hence, ability dial redox at minimum level required desired transformation renders an ideal functionalization structurally complex molecules sensitive functional groups. This strategy was, inter alia, successfully applied scale-up continuous flow step-economical assembly polycyclic aromatic hydrocarbons.

Язык: Английский

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C–H activation

Nature Reviews Methods Primers, Год журнала: 2021, Номер 1(1)

Опубликована: Июнь 17, 2021

Язык: Английский

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Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(40), С. 13163 - 13166

Опубликована: Авг. 17, 2018

Abstract For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts cathodic hydrogen (HER). Therefore, developing an alternative with accelerating kinetics to produce value‐added chemicals, especially coupled HER, is of great importance. Now, a thermodynamically more favorable primary amine (−CH 2 −NH ) electrooxidation catalyzed by NiSe nanorod arrays in reported replace OER for enhancing HER. The increased H production can be obtained at cathode; meanwhile, variety aromatic and aliphatic amines are selectively electrooxidized nitriles good yields anode. Mechanistic investigations suggest that Ni II /Ni III may serve as redox active species transformation. Hydrophobic nitrile products readily escape from aqueous electrolyte/electrode interface, avoiding deactivation catalyst thus contributing continuous gram‐scale synthesis.

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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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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Copper-Catalyzed Electrochemical C–H Amination of Arenes with Secondary Amines

Journal of the American Chemical Society, Год журнала: 2018, Номер 140(36), С. 11487 - 11494

Опубликована: Авг. 30, 2018

Electrochemical oxidation represents an environmentally friendly solution to conventional methods that require caustic stoichiometric chemical oxidants. However, C–H functionalizations merging transition-metal catalysis and electrochemical techniques are, date, largely confined the use of precious metals divided cells. Herein, we report first examples copper-catalyzed aminations arenes at room temperature using undivided cells, thereby providing a practical for construction arylamines. The n-Bu4NI as redox mediator is crucial this transformation. On basis mechanistic studies including kinetic profiles, isotope effects, cyclic voltammetric analyses, radical inhibition experiments, reaction appears proceed via single-electron-transfer (SET) process, high valent Cu(III) species likely involved. These findings provide new avenue transition-metal-catalyzed functionalization reactions mediators.

Язык: Английский

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Recent Advances in Organic Electrochemical C—H Functionalization

Chinese Journal of Chemistry, Год журнала: 2018, Номер 36(4), С. 338 - 352

Опубликована: Янв. 17, 2018

Organic electrochemistry has a rich history in organic synthesis and been considered as promising alternative to traditional chemical oxidants reductants because it obviates the use of stoichiometric amount dangerous toxic reagents. In particular, electrochemical C—H bonds functionalization is one most desirable approaches for construction carbon–carbon (C—C) carbon–heteroatom (C—X) bonds. This review summarizes substantial progress made last few years via electrochemistry. It divided into sections on C—C, C—N, C—O, C—S, C–Halogen C—P bond formation.

Язык: Английский

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Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts

Science Bulletin, Год журнала: 2021, Номер 66(23), С. 2412 - 2429

Опубликована: Июль 13, 2021

Язык: Английский

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Electrochemical C−H Amination by Cobalt Catalysis in a Renewable Solvent

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(18), С. 5090 - 5094

Опубликована: Март 6, 2018

Syntheses of substituted anilines primarily rely on palladium-catalyzed coupling chemistry with prefunctionalized aryl electrophiles. While oxidative aminations have emerged as powerful alternatives, they largely produce undesired metal-containing by-products in stoichiometric quantities. In contrast, described herein is the unprecedented electrochemical C-H amination by cobalt-catalyzed activation. The environmentally benign electrocatalysis avoids metal oxidants, can be conducted under ambient air, and employs a biomass-derived, renewable solvent for sustainable an atom- step-economical manner H2 sole byproduct.

Язык: Английский

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