A comparison of skeletal rearrangement reactions of even-electron anions in solution and in the gas phase

Eichinger, P.; Dua, Suresh; Bowie, John H.

doi:10.1016/0168-1176(94)03953-4

Cited by 35 publications

(14 citation statements)

References 81 publications

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“…3,4 In general, its initiation requires the aromatic ring system to be activated to nucleophilic attack by electron-withdrawing groups such as nitro, sulfonyl and halogen, etc. However, gas-phase studies on a model system, PhO(CH 2 ) n O À (n ¼ 2-4), carried out by Eichinger et al, [5][6][7] suggested that the Smilesrearrangement can be initiated upon collisional activation without any electron-withdrawing substituents.Morerecently,similar rearrangement reactions were also reported by Guo et al in sustained off-resonance irradiation collisioninduced dissociation (SORI-CID) studies on 2-pyrimidinyloxy-N-arylbenzylamine derivatives. and acetamide backbone, the deprotonated molecules of GW4511 and GW4751, produced in negative ESI-MS mode, predominantly dissociated to yield a benzophenoxide anion via the gas-phase S N i reaction and an intramolecular rearrangement product ion via the Smiles rearrangement reaction, upon collisional activation.…”

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confidence: 99%

Collision‐induced gas‐phase Smiles rearrangement in phenoxy‐N‐phenylacetamide derivatives

Wang

2006

Rapid Comm Mass Spectrometry

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confidence: 99%

Collision‐induced gas‐phase Smiles rearrangement in phenoxy‐N‐phenylacetamide derivatives

Wang

2006

Rapid Comm Mass Spectrometry

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“…By contrast, electron-withdrawing groups on the phenyl moiety retarded the Claisen rearrangement and gave fragment ion at m/z 175 by loss of neutral radicals of the phenyl substituents and fragment ion at m/z 160 by further loss of ·CH 3 . This report of the intrinsic reactivity of these compounds (1)(2)(3)(4)(5)(6)(7)(8) to form indoline derivatives is novel, and could be used to investigate new solution phase chemical transformations of these reactive compounds to indoline derivatives.…”

Section: Resultsmentioning

confidence: 99%

“…With a strong electron withdrawing group, such as NO 2 + were ion at m/z 175 formed by loss of neutral substituent radicals (·NO 2 or ·CF 3 ), and ion at m/z 160 formed by further loss of ·CH 3 , in similar dissociation pathways to 5·H…”

Section: Gas Phase Amide Claisen Rearrangement Reactions Of Protonatementioning

confidence: 99%

“…Recently, we reported many interesting gas phase reactions and related aromatic substitution rearrangement reactions, including benzyl migration [11], Cope rearrangement [11], Smiles rearrangement [12], metal cation catalyzed Smiles rearrangement [13,14], gas phase rearrangement of the p-aminophenylsulfonyl cation [15], sulfonyl-sulfinate rearrangement [16], retroMichael type fragmentation [17], and gas phase Favorskii rearrangement [18]. Certain analogies between reaction mechanisms in the gas phase and solution have been known for a long time [1][2][3][4][5][6][7][8][9][10]19]. The reactivities and behaviors of ionic species in the gas phase and in solution can be correlated [12,[20][21][22], and there is a significant association between gas phase reactions and the analogous reactions in solution.…”

Section: Introductionmentioning

confidence: 99%

“…T andem mass spectrometry provides extensive structural information about organic molecules, and is an important tool for mechanistic studies in gas phase organic chemistry [1][2][3][4][5][6][7][8][9][10]. Information about the energetics of gas phase reactions and fragmentation pathways can be investigated by adjusting the collision energy, the timescale of dissociation, and the collision gas.…”

Section: Introductionmentioning

confidence: 99%

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Gas Phase Decarbonylation and Cyclization Reactions of Protonated N-Methyl-N-Phenylmethacrylamide and Its Derivatives Via an Amide Claisen Rearrangement

Wang

Zhu

et al. 2012

J. Am. Soc. Mass Spectrom.

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Gas phase decarbonylation and cyclization reactions of protonated N-methyl-N-phenylmethacrylamide and its derivatives (M·H + ) were studied by electrospray ionization-tandem mass spectrometry (ESI-MS/MS). MS/MS experiments of M·H + showed product ions were formed by loss of CO, which could only occur with an amide Claisen rearrangement. Mechanisms for the gas phase decarbonylation and cyclization reactions were proposed based on the accurate m/z measurements and MS/MS experiments with deuterated compounds. Theoretical computations showed the gas phase Claisen rearrangement was a major driving force for initiating gas phase decarbonylation and cyclization reactions of M·H + . Finally, the influence of different phenyl substituents on the gas phase Claisen rearrangement was evaluated. Electron-donating groups at the para-position of the phenyl moiety promoted the gas phase Claisen rearrangement to give a high abundance of fragment ions [M − CO + H] + . By contrast, electron-withdrawing groups on the phenyl moiety retarded the Claisen rearrangement, but gave a fragment ion at m/z 175 by loss of neutral radicals of substituents on the phenyl, and a fragment ion at m/z 160 by further loss of a methyl radical.

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Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

Chen

2009

Reactive Intermediates

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Mass spectrometry (MS), originally developing from nineteenth-century physics, has a history dating back more than a hundred years. Since then, the technique has advanced enormously. The advent of new methods of ion production, novel mass analyzers, and new tools for data processing has made it possible to analyze almost all chemical entities, ranging from small organic compounds to large biological molecules and whole living cells/tissues. Today, mass spectrometry has become one of the most powerful and popular modern physical-chemical methods to study the details of elemental and molecular processes in nature. Because of its unparalleled capability of providing information on molecular weight, chemical structures, isotopic content, and even molecular dynamics, mass spectrometry is playing an increasingly significant role in the chemical and life sciences. As a traditional analytical tool and a booming technology for biomedicine, it has found extensive applications in nearly every discipline involving chemical analysis such as petroleum prospecting and refining, food processing, drug discovery, metablomics, genomics, proteomics and structural biology, as well as the environment, public safety, and industrial process monitoring. Along with the development of mass spectrometric technology, the chemistry of gaseous ions has been explored by the study of unimolecular and collision-induced dissociation (CID) [1][2][3][4] and by the study of ion/molecule reactions [2,[5][6][7][8][9][10][11][12][13][14][15][16][17] and ion/ion reactions [18][19][20][21][22][23][24][25][26] in the gas phase. The study of gas-phase ion chemistry has both fundamental and practical significance because it not only provides diverse information on ion reactivity, thermochemistry, and dynamics, but it also forms one basis for chemical analysis using mass spectrometry. In addition, the ion reactivity examined in the isolated gas-phase environment of mass spectrometers has a strong connection with reaction chemistry in solution, as well as contrasting with it. Many important ionic intermediates which are hard to probe in the condensed phase can be easily accessed in the gas phase. Therefore, mass spectrometry has also become an important and unique tool for the mechanistic investigation of organic reactions (particularly organometallic reactions), since soft electrospray ionization (ESI) technology [27, 28] became available. In this regard, there is a large body of work in the literature, which is reviewed in this book. j37This chapter will provide an overview of the history and the current state of the art of mass spectrometry-based study of ion chemistry, specifically of ion/molecule reactions. As this is a broad topic with an immense literature (over 15 000 papers), our emphasis will be placed on the applications of ESI-MS coupled with gas-phase ion/ molecule reactions and tandem mass spectrometry in organometallic chemistry, including probing key intermediates and reaction pathways of organometallic reactions in solution. We will start with...

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A comparison of skeletal rearrangement reactions of even-electron anions in solution and in the gas phase

Cited by 35 publications

References 81 publications

Collision‐induced gas‐phase Smiles rearrangement in phenoxy‐N‐phenylacetamide derivatives

Collision‐induced gas‐phase Smiles rearrangement in phenoxy‐N‐phenylacetamide derivatives

Gas Phase Decarbonylation and Cyclization Reactions of Protonated N-Methyl-N-Phenylmethacrylamide and Its Derivatives Via an Amide Claisen Rearrangement

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

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