Medium- and Sensitizer-Dependent Radical Cation Reactions: Deprotonation in Fluid Solution and Solid Matrices.

Roth, Heinz D.; Weng, Hengxin; Zhou, Dahui; Lakkaraju, Prasad S.; Sousa, Antonio; Гарновский, А. Д.; Гарновский, Д. А.; Roos, Björn O.; Vallance, Claire; Wood, Bryan R.

doi:10.3891/acta.chem.scand.51-0626

Cited by 21 publications

(20 citation statements)

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“…However, radical cation 2 ț + could be detected and characterized through pulse radiolysis of anethole (2) by UV spectroscopy [13,14,15], photoinduced electron transfer of 2 on triplet quinone by CIDNP [16,17] and in zeolite Na ZSM-5, by ESR and CIDNP [18], and by cyclic voltammetry [19]. Despite of some efforts, radical cation 3 ț + could not be detected directly by any method in solution so far [13,14].…”

Section: Sven Meyer · Jürgen O Metzgermentioning

confidence: 99%

Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

Meyer

Metzger

2003

Analytical and Bioanalytical Chemistry

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Electrospray ionization mass spectrometry (ESI-MS) coupled to a microreactor is an excellent tool for the investigation of reactions in solution. Here, we report the first results of our investigations into preparatively interesting electron-transfer-initiated chain reactions in solution which proceed via radical cations as reactive intermediates. The tris(p-bromophenyl)aminium hexachloroantimonate (1)-mediated [2+2] cycloaddition of trans-anethole (2) to give 1,2-bis(4-methoxyphenyl)-3,4-dimethylcyclobutane (3) was investigated. The reaction proceeds as a radical cation chain reaction via transient intermediates 2*+ and 3*+ that could be detected and characterized unambiguously directly in the reacting solution by ESI-MS/MS. The identity of the intermediates was confirmed by comparison with authentic MS/MS spectra of 2*+ and 3*+ obtained by atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In addition, substrate and product can be monitored easily in the reacting solution by APCI-MS.

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Section: Sven Meyer · Jürgen O Metzgermentioning

confidence: 99%

Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

Meyer

Metzger

2003

Analytical and Bioanalytical Chemistry

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“…This view is supported by the ready conversion of 5 and 6 to 7. [47] Deprotonation may become the major reaction for substrates with doubly activated 1 H nuclei, including doubly allylic ones and those between an unsaturated and a cyclopropane moiety. The oneelectron oxidation of 5 and 6 is entirely reasonable in view of the energetics delineated above.…”

Section: Discussionmentioning

confidence: 99%

Triphenylpyrylium Tetrafluoroborate-Sensitized Photochemistry of the Terpenes Sabinene, α-Phellandrene, and α- and γ-Terpinene

Climent

Miranda²,

Roth³

2000

Eur. J. Org. Chem.

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“…Instead one-electron oxidation leads to products derived from ring-opened distonic radical cations. [14][15][16][17] On the other hand, cyclobutanes have also been found to undergo cycloreversion on oxidation; [18][19][20][21] the distonic radical cations which arise as primary products of the cleavage of a single bond in ionized cyclobutanes often show interesting ensuing rearrangements. [22,23] Three tricyclic vinylcyclobutanes that we have recently synthesized have yielded some intriguing products upon photoinduced electron transfer.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Rearrangements of Tricyclic Vinylcyclobutane Derivatives

Grota

Mattay

Piech

et al. 2006

Chemistry A European J

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Three tricyclic vinylcyclobutanes (3‐methylenetricyclo[5.3.0.02,6]decanes 1–3) have been subjected to ionization by photoinduced electron transfer in solution and by X‐irradiation in Ar matrices. All three compounds undergo oxidative cycloreversion; the cleavage of the four‐membered ring, however, occurs in a different direction depending on the presence of a methyl group in position 6 of the tricyclic framework. In those derivatives, cycloreversion is found to lead to 1‐methyl‐8‐methylene‐1,6‐cyclodecadiene radical cations (5.+ from 1, 8.+ from 2) which upon back electron transfer yield two different hydrocarbons (6 from 5.+, 9 from 8.+), depending on the configuration around the endocyclic double bonds of the respective cyclodecadiene derivative. In the absence of a methyl group on C6, the cycloreversion leads to a radical cation complex between 1‐methylenecyclopent‐2‐ene and cyclopentene (12.+) which appears to revert to 3 on back electron transfer. The intermediate radical cations 5.+, 8.+, and 12.+ have been identified and characterized by UV/Vis and IR spectra in Ar matrices. The mechanism of their formation is elucidated by quantum chemical calculations.

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Medium- and Sensitizer-Dependent Radical Cation Reactions: Deprotonation in Fluid Solution and Solid Matrices.

Cited by 21 publications

References 0 publications

Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

Triphenylpyrylium Tetrafluoroborate-Sensitized Photochemistry of the Terpenes Sabinene, α-Phellandrene, and α- and γ-Terpinene

Oxidative Rearrangements of Tricyclic Vinylcyclobutane Derivatives

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