Nickel-catalyzed electrochemical homocoupling of alkenyl halides: rates and mechanisms

Cannes, Céline; Labbé, Éric; Durandetti, Muriel; Devaud, Marguerite; Nédélec, Jean‐Yves

doi:10.1016/0022-0728(96)04605-0

Cited by 58 publications

(47 citation statements)

References 19 publications

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“…Interestingly, the nature of the ligand was proven to affect the product distribution in the nickel‐catalyzed electrochemical carboxylation of terminal alkynes, suggesting that different intermediates are obtained from different Ni‐ligand couples. This assumption was more quantitatively verified in the electrochemical coupling of vinylic halides, where the reversibility of the Ni II /Ni 0 was used in the CVs to calculate the rate constants and establish both their dependence on the nature of the halogen atom and also on the Ni‐bipyridine stoichiometry (Table ).…”

Section: Electrochemical Determination Of the Redox State Stability mentioning

confidence: 95%

“…This competitive situation was also encountered in the CoBr 2 bpy catalyzed vinylation of aromatic halides, [11] where the vinyl acetate both stabilized the Co(I) complex and reacted on Figure 7. Linear sweep voltammetry at a rotating disk electrode (ω = 2000 rpm, scan rate 20 mV s À 1 ) illustrating the successive rate determining steps in the nickel-catalyzed homocoupling of vinylic halides [29] .…”

Section: Electrochemical Characterization Of Complex Reaction Sequencmentioning

confidence: 99%

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Fundamental Input of Analytical Electrochemistry in the Determination of Intermediates and Reaction Mechanisms in Electrosynthetic Processes

Labbé

Buriez

2019

ChemElectroChem

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Electroanalytical techniques like cyclic voltammetry allow convenient and fast identification of the redox status and stability of intermediates generated at electrodes in electrosynthetic processes. Accordingly, reliable mechanistic features can also be derived from the electrochemical characterization of the reactive species, and in some cases, complete and complex mechanisms can be disclosed. This Minireview highlights some representative examples taken from metal‐catalyzed electro‐reductive processes where simple electrochemical approaches provide essential information on the nature and the fate of the species formed. A special focus is made on cobalt‐promoted electrosynthetic processes, owing to the broad range of situations they display towards the stability of electrogenerated species, their reactivity, and the possible follow‐up reactions.

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Section: Electrochemical Determination Of the Redox State Stability mentioning

confidence: 95%

Section: Electrochemical Characterization Of Complex Reaction Sequencmentioning

confidence: 99%

Fundamental Input of Analytical Electrochemistry in the Determination of Intermediates and Reaction Mechanisms in Electrosynthetic Processes

Labbé

Buriez

2019

ChemElectroChem

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“…2) [28,31,32]. In the presence of aryl bromides, the anodic component of the first wave (C 1 ) disappears, and two new waves (C 3 and C 4 ) emerge at more negative potentials.…”

Section: Preparative (Electro)chemistry and Electrochemical Investigamentioning

confidence: 97%

Electron transfer in organonickel complexes of α-diimines: Versatile redox catalysts for C–C or C–P coupling reactions – A review

Klein

Budnikova

Sinyashin

2007

Journal of Organometallic Chemistry

104

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“…Subsequent capture of the alkyl radical at Ni(II) would then yield high-valent Ni(III) intermediate 9 , which was expected to undergo reductive elimination to generate the desired cross-coupled product 10 and Ni(I) complex 11 . From here, reduction of 11 [ E red > −1.10 V (24, 25)] by the reduced form of the photocatalyst 8 [ E ox = +1.37 V (21)] would regenerate both the Ni(0) catalyst 1 and the Ir catalyst 4 , closing the dual catalytic cycle.…”

mentioning

confidence: 93%

Single-electron transmetalation in organoboron cross-coupling by photoredox/nickel dual catalysis

Tellis

Primer

Molander

2014

Science

1,111

623

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The routine application of Csp3-hybridized nucleophiles in cross-coupling reactions remains an unsolved challenge in organic chemistry. The sluggish transmetalation rates observed for the preferred organoboron reagents in such transformations are a consequence of the two-electron mechanism underlying the standard catalytic approach. We describe a mechanistically distinct single-electron transfer-based strategy for the activation of organoboron reagents toward transmetalation that exhibits complementary reactivity patterns. Application of an iridium photoredox catalyst in tandem with a nickel catalyst effects the cross-coupling of potassium alkoxyalkyl- and benzyltrifluoroborates with an array of aryl bromides under exceptionally mild conditions (visible light, ambient temperature, no strong base). The transformation has been extended to the asymmetric and stereoconvergent cross-coupling of a secondary benzyltrifluoroborate.

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Nickel-catalyzed electrochemical homocoupling of alkenyl halides: rates and mechanisms

Cited by 58 publications

References 19 publications

Fundamental Input of Analytical Electrochemistry in the Determination of Intermediates and Reaction Mechanisms in Electrosynthetic Processes

Fundamental Input of Analytical Electrochemistry in the Determination of Intermediates and Reaction Mechanisms in Electrosynthetic Processes

Electron transfer in organonickel complexes of α-diimines: Versatile redox catalysts for C–C or C–P coupling reactions – A review

Single-electron transmetalation in organoboron cross-coupling by photoredox/nickel dual catalysis

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