Intramolecular transacylation: fragmentation of protonated molecules via ion‐neutral complexes in mass spectrometry

Tu, Ya-Ping; Huang, Yingying; Atsriku, Christian; You, You; Cunniff, Jack

doi:10.1002/rcm.4108

Cited by 39 publications

(41 citation statements)

References 70 publications

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“…The compounds selected in this study were expected to have the particular fragmentation loss of CH 2 O, which occurs when a proton migrates from the thermodynamically favored site to the key dissociative protonation site [19,23,24]. The compounds tested were selected to be representative of different kinds of molecules, including (1) ␣-aromatic heterocycle methyl benzyl ethers, and (2) substituted-benzyl benzyl ethers.…”

Section: Resultsmentioning

confidence: 99%

Ion-neutral complexes resulting from dissociative protonation: Fragmentation of α-furanylmethyl benzyl ethers and 4-N,N-dimethylbenzyl benzyl ethers

Liu

Pan

et al. 2010

J. Am. Soc. Mass Spectrom.

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Section: Resultsmentioning

confidence: 99%

Ion-neutral complexes resulting from dissociative protonation: Fragmentation of α-furanylmethyl benzyl ethers and 4-N,N-dimethylbenzyl benzyl ethers

Liu

Pan

et al. 2010

J. Am. Soc. Mass Spectrom.

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“…Consequently, a need for other examples of INC-mediated reactions is evident in order to better understand the fragmentation reactions in the contemporary ESI mass spectrometry, a method that has become one of the most popular analytical methods. Thus, renewed interest in studies on INC-mediated fragmentation reactions has emerged in recent years [8,[20][21][22][23][24][25][39][40][41][42][43][44][45][46][47].…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Chemistry of Benzyl Cations in Dissociation ofN-Benzylammonium andN-Benzyliminium Ions Studied by Mass Spectrometry

Chai

Wang

Sun

et al. 2012

J. Am. Soc. Mass Spectrom.

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In this study, the fragmentation reactions of various N-benzylammonium and N-benzyliminium ions were investigated by electrospray ionization mass spectrometry. In general, the dissociation of N-benzylated cations generates benzyl cations easily. Formation of ion/neutral complex intermediates consisting of the benzyl cations and the neutral fragments was observed. The intra-complex reactions included electrophilic aromatic substitution, hydride transfer, electron transfer, proton transfer, and nucleophilic aromatic substitution. These five types of reactions almost covered all the potential reactivities of benzyl cations in chemical reactions. Benzyl cations are well-known as Lewis acid and electrophile in reactions, but the present study showed that the gas-phase reactivities of some suitably ring-substituted benzyl cations were far richer. The 4-methylbenzyl cation was found to react as a Brønsted acid, benzyl cations bearing a strong electron-withdrawing group were found to react as electron acceptors, and parahalogen-substituted benzyl cations could react as substrates for nucleophilic attack at the phenyl ring. The reactions of benzyl cations were also related to the neutral counterparts. For example, in electron transfer reaction, the neutral counterpart should have low ionization energy and in nucleophilic aromatic substitution reaction, the neutral counterpart should be piperazine or analogues. This study provided a panoramic view of the reactions of benzyl cations with neutral N-containing species in the gas phase.

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“…The fragmentation reactions of organic compounds in multi-stage mass spectrometry are directly related to their structures, but the interpretation of mass spectra is not always straightforward because of many rearrangements that take place during fragmentation. In recent years, considerable research in ESI-MS has focused on studying the skeletal rearrangements of organic compounds, including alkyl transfer [24,25], benzyl cation transfer [26][27][28][29][30], benzoyl cation transfer [31], phosphate group migration [32], intramolecular electrophilic substitution [33,34], tosyl cation transfer [35], and ion/neutral complexmediated fragmentations [36][37][38][39].…”

mentioning

confidence: 99%

Intramolecular Halogen Transfer via Halonium Ion Intermediates in the Gas Phase

Chai

Xiong²,

Yue

et al. 2015

J. Am. Soc. Mass Spectrom.

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Abstract. The fragmentation of halogen-substituted protonated amines and quaternary ammonium ions (R . A potential energy surface scan using DFT calculation for CH 2 -N bond cleavage process of protonated 2-bromo-N,N-dimethylethanamine supports the formation of this intermediate. The bromonium ion intermediate-involved halogen transfer mechanism is supported by an examination of the ion/molecule reaction between isolated ethylenebromonium ion and triethylamine, which generates the N-bromo-N,N,N-triethylammonium cation. For other halogens, Cl and I also can be involved in similar intramolecular halogen transfer, but F cannot be involved. With the elongation of the carbon chain between the halogen (bromine as a representative example) and amine, the migration ability of halogen decreases. When the carbon chain contains two or three CH 2 units (n = 1, 2), formal bromine cation transfer can take place, and the transfer is easier when n = 1. When the carbon chain contains four or five CH 2 units (n = 3, 4), formal bromine cation transfer does not occur, probably because the fiveand six-membered cyclic bromonium ions are very stable and do not donate the bromine to the amine.

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Intramolecular transacylation: fragmentation of protonated molecules via ion‐neutral complexes in mass spectrometry

Cited by 39 publications

References 70 publications

Ion-neutral complexes resulting from dissociative protonation: Fragmentation of α-furanylmethyl benzyl ethers and 4-N,N-dimethylbenzyl benzyl ethers

Ion-neutral complexes resulting from dissociative protonation: Fragmentation of α-furanylmethyl benzyl ethers and 4-N,N-dimethylbenzyl benzyl ethers

Gas-Phase Chemistry of Benzyl Cations in Dissociation ofN-Benzylammonium andN-Benzyliminium Ions Studied by Mass Spectrometry

Intramolecular Halogen Transfer via Halonium Ion Intermediates in the Gas Phase

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