Electrochemical Arylation of Electron‐Deficient Arenes through Reductive Activation

Wang, Pan; Yang, Zhenlin; Wang, Ziwei; Xu, Chenyang; Huang, Lei; Wang, Shengchun; Zhang, Heng; Lei, Aiwen

doi:10.1002/ange.201909600

Cited by 16 publications

(5 citation statements)

References 56 publications

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“…Specifically, Zhang et al employed diazonium tetrafluoroborates for the electrochemical arylation of electron-deficient arenes (Scheme 24a). 97 In this transformation, salts possessing electron-donating or withdrawing groups were reactive, although the latter featured reduced yields. A broad range of electron-deficient arenes, including quinoxalines, quinoxalinones, pyrazines, and other N-heteroarenes, were also tolerated.…”

Section: Electrochemistrymentioning

confidence: 95%

Modern Photo- and Electrochemical Approaches to Aryl Radical Generation

Grudzień,

Zlobin,

Zadworny

et al. 2024

Preprint

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Aryl rings appear in a plethora of natural products or drugs. A vast majority of arylation processes still rely on the utilization of transition-metal complexes as catalysts. Another important strategy for introducing aryl rings into an organic skeleton operate through a radical pathway. The chemistry of aryl radicals has witnessed rapid development during the last century, especially as these species are crucial intermediates in many synthetically-meaningful organic transformations, such as the Sandmeyer or Pschorr reactions. Predominately, they are prepared employing conventional redox reagents (oxidants or reductans) that are often used in large excess. In turn, recent developments in photocatalysis and synthetic electrochemistry allow for the assembly of Ar• species in a more sustainable and straightforward way, however, these advancements have not been timely and critically summarised so far. This Review fills this obvious gap and sum up recent advances in processes involving Ar• by highlighting some challenges and identifying potential areas of improvement, which might inspire future research endeavors in this topic.

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Section: Electrochemistrymentioning

confidence: 95%

Modern Photo- and Electrochemical Approaches to Aryl Radical Generation

Grudzień,

Zlobin,

Zadworny

et al. 2024

Preprint

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“…Additionally, electron-de cient N-heteroarenes are prone to accept an electron to generate the corresponding radical anion under cathodic reduction conditions. 32 To investigate the reduction behavior of 1a, LSV curves are recorded in anhydrous acetonitrile (AN) containing tetrabutylammonium tetra uoroborate (TBABF 4 ) as the electrolyte over an inert glass carbon cathode. Fig.…”

Section: Mechanistic Studiesmentioning

confidence: 99%

“…Therefore, we deduce that the electrocatalytic hydrogenation of 1a begins with 1a gaining an electron, which is similar to Lei's work. 32 Furthermore, in situ formed H* via H 2 O dissociation is proven to be the key species in electrocatalytic transfer hydrogenation reactions. [23][24][25]29 Electron paramagnetic resonance (EPR) measurements with 5,5dimethyl-1-pyrroline-N-oxide (DMPO) as the radical spin-trapping reagent con rm the generation of hydrogen radicals (Fig.…”

Section: Mechanistic Studiesmentioning

confidence: 99%

“…However, the yields of coupling products of quinoline derivatives are low. 32 We speculate that these inferior performances may be ascribed to the lack of suitable materials to effectively activate quinolines. Given the importance of THQs and related compounds, it is highly desirable to synthesize an advanced material to e ciently promote the activation of quinolines and water, which will be conducive to boosting the activity and selectivity of quinolines hydrogenation.…”

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confidence: 99%

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Fluorine-modified cobalt electrocatalyst for quinoline hydrogenation with water at room temperature

Guo

Wang

et al. 2022

Preprint

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The room temperature selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines (THQs) using a safe and clean hydrogen donor catalyzed by cost-effective catalysts is significant but challenging because of the difficult activation of quinolines and H2. Here, a fluorine-modified cobalt catalyst is synthesized via electroreduction of Co(OH)F precursor that exhibits high activity for electrocatalytic hydrogenation of quinolines by using H2O as the hydrogen source to produce THQs with up to 99% selectivity and 94% isolated yield under ambient conditions. F is revealed to enhance the adsorption of quinolines, and promote water activation to produce active atomic hydrogen (H*) by forming F−-K+(H2O)7 networks. A unique 1,4/2,3-addition pathway involving H* is proposed by combining experimental and theoretical results. Wide substrate scopes, scalable synthesis of bioactive precursors, expedient fabrication of deuterated analogues, and paired synthesis of tetrahydroquinoline and industrially important adiponitrile at a low voltage highlight the promising application of this methodology.

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“…In this regard, Lei and co-workers in 2019 reported an electrochemical arylation of electron-deficient arenes through reductive activation (Fig. 8A, ii ) 107 . The reaction proceeds through the given plausible mechanism (Fig.…”

Section: Introductionmentioning

confidence: 97%

Traditional and sustainable approaches for the construction of C–C bonds by harnessing C–H arylation

et al. 2022

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Biaryl scaffolds are found in natural products and drug molecules and exhibit a wide range of biological activities. In past decade, the transition metal-catalyzed C–H arylation reaction came out as an effective tool for the construction of biaryl motifs. However, traditional transition metal-catalyzed C–H arylation reactions have limitations like harsh reaction conditions, narrow substrate scope, use of additives etc. and therefore encouraged synthetic chemists to look for alternate greener approaches. This review aims to draw a general overview on C–H bond arylation reactions for the formation of C–C bonds with the aid of different methodologies, majorly highlighting on greener and sustainable approaches.

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Electrochemical Arylation of Electron‐Deficient Arenes through Reductive Activation

Cited by 16 publications

References 56 publications

Modern Photo- and Electrochemical Approaches to Aryl Radical Generation

Modern Photo- and Electrochemical Approaches to Aryl Radical Generation

Fluorine-modified cobalt electrocatalyst for quinoline hydrogenation with water at room temperature

Traditional and sustainable approaches for the construction of C–C bonds by harnessing C–H arylation

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