Mesolysis Mechanisms of Aromatic Thioether Radical Anions Studied by Pulse Radiolysis and DFT Calculations

Yamaji, Minoru; Tojo, Sachiko; Fujitsuka, Mamoru; Sugimoto, Akihiro; Majima, Tetsuro

doi:10.1021/acs.joc.5b00660

Cited by 7 publications

(3 citation statements)

References 24 publications

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“…These include, for example, the formation of Grignard reagents, [5] S RN 1 reactions, [6,7] DNA damage, [8,9] and enzymatic reactions [10] . They are also used for the synthesis of materials [11,12] for various applications and have understandably been intensively investigated both experimentally [5–12] and theoretically [13,14] . Of particular importance is the understanding of the effect of substituents on the formation and subsequent dissociation of radical ions.…”

Section: Introductionmentioning

confidence: 99%

New Insights into the Substituents’ Effect on the Formation and Dissociation of Radical Anions: Dissociative Electron Transfer to Arylsulfonylphthalimides

2021

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The electrochemical reduction of a series of biologically relevant p‐substituted arylsulfonylphthalimides was investigated and the results were analysed using theoretical calculations and application of Savéant's dissociative electron transfer theory. The dissociation rate constants of the radical anion intermediates were calculated and showed that upon changing the substituent from the MeO, to Me, H, F, Cl and CN the dissociation became faster. A good correlation with the Hammett substituent constants was also obtained. With the NO2 substituent the trend was however inversed. These results and the electrolysis data showed that the dissociation involves the N−S chemical bond. Theoretical calculations showed that for all investigated compounds the extra electron was hosted by the phthalimidyl group except for the p‐NO2 substituted compound for which the extra electron was hosted by the nitrophenyl moiety. Thermodynamic considerations showed that the dissociation of the radical anion of the p‐NO2 compound followed a heterolytic cleavage whereas those of the rest of the investigated compounds followed a homolytic cleavage. The above intriguing result was rationalized through application of the extension of Savéant's dissociative electron transfer theory to the decomposition of radical anions. This study is important not only for understanding substituents’ effect on the biological activity of these compounds but also on the formation and dissociation of radical anions in general.

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Section: Introductionmentioning

confidence: 99%

New Insights into the Substituents’ Effect on the Formation and Dissociation of Radical Anions: Dissociative Electron Transfer to Arylsulfonylphthalimides

2021

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“…We have studied the mesolysis of aromatic compounds with S – S, 21 Se–Se, 32 C–O, 33 and C–S bonds. 34 Based on the results, exothermic bond dissociation energies (BDE) of the σ-bonds are required for the occurrence of mesolysis in these parent radical anions. In the present work, we evaluated BDEs of the S – S bond in XSSX˙ − by using eqn (4).Δ H f (RA) = Δ H f (Rad) +Δ H f (Ani) – BDE(S – S)Here, Δ H f (RA), Δ H f (Rad), and Δ H f (Ani) denote the heats of formation for the radical anion, radical, and anion of XSSX, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…We have studied the mesolysis of aromatic compounds with S-S, 21 Se-Se, 32 C-O, 33 and C-S bonds. 34 Based on the results, exothermic bond dissociation energies (BDE) of the s-bonds are required for the occurrence of mesolysis in these parent radical anions. In the present work, we evaluated BDEs of the S-S bond in XSSX À by using eqn (4).…”

Section: S-s Bond Dissociation Energy In Radical Anions By Dft Calcul...mentioning

confidence: 99%

Mesolysis of an asymmetric diphenyldisulfide radical anion studied by γ-ray and pulsed-electron radiolyses

Yamaji

Tojo

Majima

et al. 2023

Phys. Chem. Chem. Phys.

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Electroreductive Desulfurative Transformations with Thioethers as Alkyl Radical Precursors**

et al. 2023

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Thioethers are highly prevalent functional groups in organic compounds of natural and synthetic origin but remain remarkably underexplored as starting materials in desulfurative transformations. As such, new synthetic methods are highly desirable to unlock the potential of the compound class. In this vein, electrochemistry is an ideal tool to enable new reactivity and selectivity under mild conditions. Herein, we demonstrate the efficient use of aryl alkyl thioethers as alkyl radical precursors in electroreductive transformations, along with mechanistic details. The transformations proceed with complete selectivity for C(sp3)−S bond cleavage, orthogonal to that of established transition metal‐catalyzed two‐electron routes. We showcase a hydrodesulfurization protocol with broad functional group tolerance, the first example of desulfurative C(sp3)−C(sp3) bond formation in Giese‐type cross‐coupling and the first protocol for electrocarboxylation of synthetic relevance with thioethers as starting materials. Finally, the compound class is shown to outcompete their well‐established sulfone analogues as alkyl radical precursors, demonstrating their synthetic potential for future desulfurative transformations in a one‐electron manifold.

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Mesolysis Mechanisms of Aromatic Thioether Radical Anions Studied by Pulse Radiolysis and DFT Calculations

Cited by 7 publications

References 24 publications

New Insights into the Substituents’ Effect on the Formation and Dissociation of Radical Anions: Dissociative Electron Transfer to Arylsulfonylphthalimides

New Insights into the Substituents’ Effect on the Formation and Dissociation of Radical Anions: Dissociative Electron Transfer to Arylsulfonylphthalimides

Mesolysis of an asymmetric diphenyldisulfide radical anion studied by γ-ray and pulsed-electron radiolyses

Electroreductive Desulfurative Transformations with Thioethers as Alkyl Radical Precursors**

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