Theoretical insight into decatungstate photocatalyzed alkylation of<i>N</i>-tosylimine<i>via</i>hydrogen atom transfer and proton-coupled electron transfer

Meng, Liang; Dong, Yujiao; Zhu, Bo; Liang, Yujie; Su, Zhong‐Min; Guan, Wei

doi:10.1039/d2dt00927g

Dalton Trans.

2022

DOI: 10.1039/d2dt00927g

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Theoretical insight into decatungstate photocatalyzed alkylation ofN-tosylimineviahydrogen atom transfer and proton-coupled electron transfer

Liang Meng

Yujiao Dong

Bo Zhu

et al.

Abstract: Decatungstate as a photocatalyst can activate various C(sp3)−H bond to successfully construct C(sp3)−C(sp2) bond with N-tosylimines. Herein density functional theory (DFT) calculations reveal the unique radical mechanism triggered by the...

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Cited by 4 publications

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“…Following the literature consensus (Figure ), , we assumed that TBADT ( [W] 4– ) is activated upon the irradiation of light. Although there are multiple oxygens in [W] 4– *, the spin density is mostly located on one of the bridging oxygen (0.93, see Part B11 in the Supporting Information), rendering it the most reactive site for C–H abstraction.…”

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confidence: 68%

Photochemical Allylation of Alkanes Enabled by Nickel Catalysis

Jin

Fan

et al. 2022

ACS Catal.

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We have developed an allylic alkylation of alkanes by dual photo-HAT/nickel catalysis. In this reaction, radical-type hydrogen-atom-transfer of the alkanes is enabled by decatungstate as a photocatalyst, whereas nickel serves to cleave the C–O bond in the substrates under mild reaction conditions. This co-catalyzed reaction provides a method for direct functionalization of alkanes. Density functional theory calculations show that reductive elimination is the rate-determining step of this reaction.

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confidence: 68%

Photochemical Allylation of Alkanes Enabled by Nickel Catalysis

Jin

Fan

et al. 2022

ACS Catal.

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Theoretical Mechanistic Study of C(sp³)−C(sp²) Cross‐Coupling by Photoredox‐Mediated Iridium(III)/Nickel(II)/Quinuclidine Triple Catalysis

Wang

et al. 2023

Chemistry An Asian Journal

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The photoredox-mediated iridium(III)/nickel(II)/3acetoxyquinuclidine triple-synergistic catalysis was comprehensively investigated by taking a C(sp 3 )À C(sp 2 ) bond crosscoupling as a reaction model using density functional theory (DFT) calculations. The synergistic mechanism of the triple catalytic system includes a reductive quenching cycle (Ir III À *Ir III À Ir II À Ir III ), an organocatalytic cycle, and a nickel catalytic cycle (Ni II À Ni I À Ni III À [Ni III ] ⊖ À Ni II ). Electronic process analysis shows that 3-acetoxyquinuclidine acts as a hydrogen atom transfer (HAT) catalyst to regioselectively provide αcarbon centered radical. Due to more favorable oxidative addition of CÀ Br to Ni(I) than HAT to avoid the formation of stable Ni(II) species, the generated α-carbon centered radical prefers to be captured by oxidative addition product Ni(III) to form an unusual [Ni III ] ⊖ C ⊕ species when 3-acetoxyquinuclidine was employed. These theoretical insights not only provide deep electronic process understanding of the photoredoxmediated iridium(III)/nickel(II) synergistic catalysis, but also clarify the electron-withdrawing group effect of quinuclidine, which has a potential guiding role for further development of new cross-coupling reactions.

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Theoretical Insight on the High Reactivity of Reductive Elimination of Ni^III Based on Energy- and Electron-Transfer Mechanisms

et al. 2023

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Iridium/nickel (Ir/Ni) metallaphotoredox dual catalysis overcomes the challenging reductive elimination (RE) of Ni(II) species and has made a breakthrough progress to construct a wide range of C–X (X = C, N, S, and P) bonds. However, the corresponding reaction mechanisms are still ambiguous and controversial because the systematic research on the nature of this synergistic catalysis is not sufficient. Herein, IrIII/NiII and IrIII/Ni0 metallaphotoredox catalysis have been theoretically explored taking the aryl esterification reaction of benzoic acid and aryl bromide as an example by a combination of density functional theory (DFT), molecular dynamics, and time-dependent DFT computations. It is found that an electron-transfer mechanism is applicable to IrIII/NiII metallaphotoredox catalysis, but an energy-transfer mechanism is applicable to IrIII/Ni0 combination. The IrIII/NiII metallaphotoredox catalysis succeeds to construct a NiI–NiIII catalytic cycle to avoid the challenging RE of Ni(II) species, while the RE occurs from triplet excited-state Ni(II) species in the IrIII/Ni0 metallaphotoredox catalysis. In addition, the lower lowest unoccupied molecular orbital energy level of Ni(III) species than that of Ni(II) species accelerates RE from Ni(III) one. The triplet excited-state Ni(II) species can resemble a Ni(III) center, considering the metal-to-ligand charge transfer character to promote the RE.

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Theoretical insight into decatungstate photocatalyzed alkylation ofN-tosylimineviahydrogen atom transfer and proton-coupled electron transfer

Abstract: Decatungstate as a photocatalyst can activate various C(sp3)−H bond to successfully construct C(sp3)−C(sp2) bond with N-tosylimines. Herein density functional theory (DFT) calculations reveal the unique radical mechanism triggered by the...

Cited by 4 publications

References 47 publications

Photochemical Allylation of Alkanes Enabled by Nickel Catalysis

Photochemical Allylation of Alkanes Enabled by Nickel Catalysis

Theoretical Mechanistic Study of C(sp³)−C(sp²) Cross‐Coupling by Photoredox‐Mediated Iridium(III)/Nickel(II)/Quinuclidine Triple Catalysis

Theoretical Insight on the High Reactivity of Reductive Elimination of Ni^III Based on Energy- and Electron-Transfer Mechanisms

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Theoretical insight into decatungstate photocatalyzed alkylation ofN-tosylimineviahydrogen atom transfer and proton-coupled electron transfer

Abstract: Decatungstate as a photocatalyst can activate various C(sp3)−H bond to successfully construct C(sp3)−C(sp2) bond with N-tosylimines. Herein density functional theory (DFT) calculations reveal the unique radical mechanism triggered by the...

Cited by 4 publications

References 47 publications

Photochemical Allylation of Alkanes Enabled by Nickel Catalysis

Photochemical Allylation of Alkanes Enabled by Nickel Catalysis

Theoretical Mechanistic Study of C(sp3)−C(sp2) Cross‐Coupling by Photoredox‐Mediated Iridium(III)/Nickel(II)/Quinuclidine Triple Catalysis

Theoretical Insight on the High Reactivity of Reductive Elimination of NiIII Based on Energy- and Electron-Transfer Mechanisms

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Product

Resources

About

Theoretical Mechanistic Study of C(sp³)−C(sp²) Cross‐Coupling by Photoredox‐Mediated Iridium(III)/Nickel(II)/Quinuclidine Triple Catalysis

Theoretical Insight on the High Reactivity of Reductive Elimination of Ni^III Based on Energy- and Electron-Transfer Mechanisms