A Non-Outer Sphere Mechanism for the Ionization of Aryl Vinyl Sulfides by Triarylaminium Salts

Bauld, Nathan L.; Aplin, J. Todd; Yueh, and Wang; Loinaz, A.

doi:10.1021/ja9706965

Cited by 23 publications

(29 citation statements)

References 26 publications

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“…This was to be expected because the oxidation potential of cyclopentadiene (3) is approximately 0.4 V higher than the respective oxidation potential of phenylvinylsulfide (2), which is oxidized by radical cation 1 •+ . 27,32 In the case of the Diels-Alder reaction of trans-anethole (5) and isoprene (6), 5 has an oxidation potential ∼0.55 V lower than that of 6, and therefore 5 was oxidized by radical cation 1 •+ . 33 Radical cations 2 •+ , 4 •+ , 5 •+ , 7 •+ , 8 •+ , and 9 •+ could not be observed in the performed control experiments in the absence of 1 •+ SbCl 6 -.…”

Section: Reaction Of Phenylvinylsulfide (2) and Cyclopentadiene (3): mentioning

confidence: 99%

“…Preparatively, this reaction experiment was carried out by the addition of a 30 mol % solution of 1 •+ SbCl 6 -in dichloromethane to a solution of 2 with 14 equiv of 3 at 0°C; the Diels-Alder cycloaddition product, 5-(phenylthio)norbornene (4), was obtained in 30% yield with an endo/exo ratio of 3:1 after a few minutes. 27 In chemical textbooks, electron-transfer (ET) processes are classified as outer sphere ETs, involving no significant covalent interactions between donor and acceptor, or inner sphere ETs, involving significant weak to strong covalent interactions between donor and acceptor. 28 Some years ago, Bauld postulated a further mechanism for the electron transfer of the tris(pbromophenyl)aminium radical cation to phenylvinylsulfide.…”

Section: Introductionmentioning

confidence: 99%

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Detection of Transient Radical Cations in Electron Transfer-Initiated Diels−Alder Reactions by Electrospray Ionization Mass Spectrometry

Fürmeier

Metzger

2004

J. Am. Chem. Soc.

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The coupling of a simple microreactor to an atmospheric pressure ion source, such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), allows the investigation of reactions in solution by mass spectrometry. The tris(p-bromophenyl)aminium hexachloroantimonate (1(*)(+)SbCl(6)(-))-initiated reactions of phenylvinylsulfide (2) and cyclopentadiene (3) and of trans-anethole (5) and isoprene (6) and the dimerization of 1,3-cyclohexadiene (8) to give the respective Diels-Alder products were studied. These preparatively interesting reactions proceed as radical cation chain reactions via the transient radical cations of the respective dienophiles and of the respective Diels-Alder addition products. These radical cations could be detected directly and characterized unambiguously in the reacting solution by ESI-MS-MS. The identity was confirmed by comparison with MS-MS spectra of the authentic radical cations obtained by APCI-MS and by CID experiments of the corresponding molecular ions generated by EI-MS. In addition, substrates and products could be monitored easily in the reacting solution by APCI-MS.

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Section: Reaction Of Phenylvinylsulfide (2) and Cyclopentadiene (3): mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Detection of Transient Radical Cations in Electron Transfer-Initiated Diels−Alder Reactions by Electrospray Ionization Mass Spectrometry

Fürmeier

Metzger

2004

J. Am. Chem. Soc.

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“…The proposed dimerization product of m / z 279, which results from the electrophilic aromatic substitution reaction, is therefore most likely 1A and/or 1B . Substituent effects are known to affect the electrophilic additions to the aromatic π bond 27–30. Product‐ 1A appears to be more stable than 1B as oxygen might be able to donate electrons to the benzene ring more efficiently than sulfur via its π electrons.…”

Section: Resultsmentioning

confidence: 99%

Dimerization of ionized 4‐(methyl mercapto)‐phenol during ESI, APCI and APPI mass spectrometry

Eberlin

Corilo

et al. 2009

J. Mass Spectrom.

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A novel ion/molecule reaction was observed to occur under electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photo ionization (APPI) conditions, leading to dimerization of ionized 4-(methyl mercapto)-phenol followed by fast H(*) loss. The reaction is particularly favored during ESI, which suggests that this ion/molecule reaction can occur both in the solution inside the ESI-charged droplets and in the gas-phase environment of most other atmospheric pressure ionization techniques. The dimerization reaction is inherent to the electrolytic process during ESI, whereas it is more by ion/molecule chemistry in nature during APCI and APPI. From the tandem mass spectrometry (MS/MS) data, accurate mass measurements, hydrogen/deuterium (H/D) exchange experiments and density functional theory (DFT) calculations, two methyl sulfonium ions appear to be the most likely products of this electrophilic aromatic substitution reaction. The possible occurrence of this unexpected reaction complicates mass spectral data interpretation and can be misleading in terms of structural assignment as reported herein for 4-(methyl mercapto)-phenol.

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“…For example, the reductive potentials of TBPA +• and tris(2,4-dibromophenyl)aminium hexachloroantimonate (TDBPA +• ) are 1.15 V and 1.66 V, respectively, versus the saturated calomel electrode (SCE). With the exception of certain cases, 6 radical cation salts have been used as well-behaved single-electron oxidants in outer-sphere electron transfer processes.…”

Section: Widely Used Radical Cation Saltsmentioning

confidence: 99%

Radical Cation Salts: From Single-Electron Oxidation to C–H Activation

Jia

2015

Synthesis

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This short review describes the work performed by my group on reactions initiated by radical cation salts. In our early studies, transformations based on single-electron oxidations induced by radical cation salts were investigated. More recently, we focused on aerobic oxidations of C-H bonds promoted by radical cation salts. In this work, we elucidate the mechanism, determine the scope, and discuss the potential future applications of radical cation salts in efficient transformations of C-H bonds.

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A Non-Outer Sphere Mechanism for the Ionization of Aryl Vinyl Sulfides by Triarylaminium Salts

Cited by 23 publications

References 26 publications

Detection of Transient Radical Cations in Electron Transfer-Initiated Diels−Alder Reactions by Electrospray Ionization Mass Spectrometry

Detection of Transient Radical Cations in Electron Transfer-Initiated Diels−Alder Reactions by Electrospray Ionization Mass Spectrometry

Dimerization of ionized 4‐(methyl mercapto)‐phenol during ESI, APCI and APPI mass spectrometry

Radical Cation Salts: From Single-Electron Oxidation to C–H Activation

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A Non-Outer Sphere Mechanism for the Ionization of Aryl Vinyl Sulfides by Triarylaminium Salts

Cited by 23 publications

References 26 publications

Detection of Transient Radical Cations in Electron Transfer-Initiated Diels−Alder Reactions by Electrospray Ionization Mass Spectrometry

Detection of Transient Radical Cations in Electron Transfer-Initiated Diels−Alder Reactions by Electrospray Ionization Mass Spectrometry

Dimerization of ionized 4‐(methyl mercapto)‐phenol during ESI, APCI and APPI mass spectrometry

Radical Cation Salts: From Single-Electron Oxidation to C–H Activation­

Contact Info

Product

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About

Radical Cation Salts: From Single-Electron Oxidation to C–H Activation