Solvatation als Ursache für die unerwartete Nucleophilie‐Reihung von Peroxid‐Anionen

Mayer, Robert J.; Tokuyasu, Takahiro; Mayer, Péter; Gomar, Jérôme; Sabelle, Stéphane; Mennucci, Benedetta; Mayr, Herbert; Ofial, Armin R.

doi:10.1002/ange.201707086

Cited by 6 publications

(3 citation statements)

References 43 publications

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“…We synthesized an alternative peracid, peroxyphenylacetic acid (PPAA), that we could isolate in pure form (> 92 %), containing only minor quantities of residual acid (Figure S10). [15] We also developed efficient and high-yielding methods for the synthesis of isotopically labelled H 2 18 O 2 and 18 O-PPAA (see Supporting Information for details).…”

Section: Preparation Of High-valent Species Supported By L Phmentioning

confidence: 99%

“…Peroxyphenylacetic acid (PPAA) and peroxypivalic (PPA) were synthesized according to literature procedures. [15,50] CAUTION: Peroxyacids are known to be potentially explosive once obtained as a dry powder. Compounds were stored at À 20 °C and never heated above 40 °C.…”

Section: Xas Data Collection and Analysismentioning

confidence: 99%

“…The target compound was synthesized by adapting a reported procedure. [15] Phenylacetic acid (156 mg, 1.15 mmol) and methanesulfonic acid (MsOH, 1.1 mL) were combined in a screw-capped tube. CH 2 Cl 2 (0.8 mL) was added and the resulting mixture was stirred to form a pale yellow solution.…”

Section: Synthesis Of 18 O-labelled Peroxyphenylacetic Acid ( 18 O-ppaa)mentioning

confidence: 99%

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Synthesis and Characterization of a Masked Terminal Nickel‐Oxide Complex

Heim

Spedalotto

Lovisari

et al. 2023

Chemistry A European J

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In exploring terminal nickel‐oxo complexes, postulated to be the active oxidant in natural and non‐natural oxidation reactions, we report the synthesis of the pseudo‐trigonal bipyramidal NiII complexes (K)[NiII(LPh)(DMF)] (1[DMF]) and (NMe4)2[NiII(LPh)(OAc)] (1[OAc]) (LPh=2,2’,2’’‐nitrilo‐tris‐(N‐phenylacetamide); DMF=N,N‐dimethylformamide; −OAc=acetate). Both complexes were characterized using NMR, FTIR, ESI‐MS, and X‐ray crystallography, showing the LPh ligand to bind in a tetradentate fashion, together with an ancillary donor. The reaction of 1[OAc] with peroxyphenyl acetic acid (PPAA) resulted in the formation of [(LPh)NiIII−O−H⋅⋅⋅OAc]2−, 2, that displays many of the characteristics of a terminal Ni=O species. 2 was characterized by UV‐Vis, EPR, and XAS spectroscopies and ESI‐MS. 2 decayed to yield a NiII‐phenolate complex 3 (through aromatic electrophilic substitution) that was characterized by NMR, FTIR, ESI‐MS, and X‐ray crystallography. 2 was capable of hydroxylation of hydrocarbons and epoxidation of olefins, as well as oxygen atom transfer oxidation of phosphines at exceptional rates. While the oxo‐wall remains standing, this complex represents an excellent example of a masked metal‐oxide that displays all of the properties expected of the ever elusive terminal M=O beyond the oxo‐wall.

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Section: Preparation Of High-valent Species Supported By L Phmentioning

confidence: 99%

Section: Xas Data Collection and Analysismentioning

confidence: 99%

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Synthesis and Characterization of a Masked Terminal Nickel‐Oxide Complex

Heim

Spedalotto

Lovisari

et al. 2023

Chemistry A European J

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Nucleophilie von Glutathion als Bindeglied zur Reaktivität von Michael‐Akzeptoren

Mayer

Ofial

2019

Angewandte Chemie

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Deprotoniertes Glutathion gehçrt zu den potentesten biologischen Nucleophilen und spielt durch die Bildung kovalenter Konjugate mit Michael-Akzeptoren eine wichtige physiologische Rolle bei der Zellentgiftung.D ie Elektrophilie Everschiedener Michael-Akzeptoren wurdekürzlichauf Basis der Patz-Mayr-Gleichung lg k 2 = s N (N + E) charakterisiert. Wirh aben nun die nucleophile Reaktivität( N, s N )v on Glutathion (GSH) in wässriger Lçsung bei 20 8 8Cb estimmt, um publizierte GSH-Reaktivitäten (k GSH )m it der Mayr-Elektrophilieskala zu verbinden. Auf diese Weise lässt sich die Elektrophilie Ev on mehr als 70 Michael-Akzeptoren abschätzen, was dazu genutzt werden kann, systematisch neue Reaktionen mit einer Vielzahl an Nucleophilen vorherzusagen, deren Nucleophilieparameter N/s N bekannt sind.Abbildung 1. In dieser Arbeit verwendete Referenzelektrophile E1-E17 (Gegenion der Benzhydrylium-Ionen E1-E4:BF 4 À ;Elektrophilieparameter E aus Lit. [10, 11b, 12]).

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Nucleophilicity of Glutathione: A Link to Michael Acceptor Reactivities

Mayer

Ofial

2019

Angew Chem Int Ed

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Deprotonated glutathione is among the most potent biological nucleophiles and plays an important physiological role in cellular detoxification by forming covalent conjugates with Michael acceptors. The electrophilicity E of various Michael acceptors was characterized recently according to the Patz–Mayr relation lg k 2=s N(N+E). We now determined the nucleophilic reactivity (N, s N) of glutathione (GSH) in aqueous solution at 20 °C to connect published GSH reactivities (k GSH) with Mayr's electrophilicity scale (E). In this way, electrophilicities E of more than 70 Michael acceptors could be estimated, which can now be used to systematically predict novel reactions with the multitude of nucleophiles whose nucleophilicity parameters N/s N are known.

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Solvatation als Ursache für die unerwartete Nucleophilie‐Reihung von Peroxid‐Anionen

Cited by 6 publications

References 43 publications

Synthesis and Characterization of a Masked Terminal Nickel‐Oxide Complex

Synthesis and Characterization of a Masked Terminal Nickel‐Oxide Complex

Nucleophilie von Glutathion als Bindeglied zur Reaktivität von Michael‐Akzeptoren

Nucleophilicity of Glutathione: A Link to Michael Acceptor Reactivities

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