Dissociation of protonated N‐(3‐phenyl‐2H‐chromen‐2‐ylidene)‐ benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer

Wang, Shanshan; Cheng, Dong; Guo, Cheng; Jiang, Kezhi

doi:10.1002/rcm.7420

Cited by 7 publications

(6 citation statements)

References 44 publications

(90 reference statements)

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“…However, most of the reports deal with the benzyl cation transfer. More recently, reports have appeared demonstrating sulfonyl cation transfer during fragmentation of protonated sulfonamides, but we are unaware of similar reports describing Friedel‐Crafts acylation. Reported ion‐molecule reactions of acylium ions within ion‐neutral complexes mostly include an intramolecular transacylation reaction in which the acylium ion migrates to attack another nucleophilic center in the molecule .…”

Section: Resultsmentioning

confidence: 94%

Collision‐induced dissociation of phenethylamides: role of ion‐neutral complexes

Nikolić

Macias

Lankin

et al. 2017

Rapid Comm Mass Spectrometry

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RATIONALE Phenethylamides are a large group of naturally occurring molecules found both in the plant and animal kingdoms. In addition, they are used as intermediates for the synthesis of pharmaceutically important dihydro- and tetrahydroisoquinolines. To enable efficient characterization of this class of molecules, a detailed mass spectrometric fragmentation study of a broad series of analogs was carried out. METHODS The test compounds were synthesized using standard methods for amide bond formation. Low energy high resolution tandem mass spectra were acquired on a hybrid quadrupole/time-of-flight mass spectrometer using positive ion electrospray ionization. RESULTS A total of 26 analogs were investigated in the study. Fragmentation of phenethylamides was found to proceed via intermediate ion-neutral complexes. The complexes can break down via multiple pathways including dissociation, proton transfer, Friedel-Crafts acylation, and single electron transfer. The relative contribution of each of these pathways strongly depends on the structure of the coupling amine and acid. CONCLUSIONS A general scheme for the fragmentation of phenethylamides was developed. This study further extends the knowledge base of the ion-neutral complex by discovering Friedel-Crafts acylation as a novel reaction. The strong influence of minor structural modifications on the fragmentation patterns highlights the importance of testing many analogs in order to fully predict a fragmentation pattern of a particular class of molecules.

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Section: Resultsmentioning

confidence: 94%

Collision‐induced dissociation of phenethylamides: role of ion‐neutral complexes

Nikolić

Macias

Lankin

et al. 2017

Rapid Comm Mass Spectrometry

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“…Substituent effects are very useful in probing reaction mechanisms ( Guo et al, 2012 ; Wang et al, 2015 ; Zhang et al, 2015 ; Wang et al, 2016 ). To better delineate the universality of the gas-phase hydroxyl transfer reaction, a series of compounds bearing different substituents (H-substituted, OCH 3 -substituted, Cl-substituted, CH 3 -substituted, OH-substituted, Br-substituted) at the para position of the phenyl ring were also investigated by tandem MS experiments (Supplementary Figure S4-10), and the tandem MS data were summarized in Table 2 .…”

Section: Resultsmentioning

confidence: 99%

“…In particular, tandem mass spectrometry can offer abundant fragmentation data for structure elucidation, which is acted as a small “gas-phase chemistry laboratory”. Several specific rearrangement reactions have been reported in tandem mass spectrometry, including hydride transfer ( Chai et al, 2010 ), benzyl cation transfer ( Sun et al, 2012 ; Li et al, 2014 ; Paulose et al, 2015 ), sulfonyl cation transfer ( Wang et al, 2016 ), methyl transfer ( Kshirsagar and Argade, 2009 ; Ren et al, 2019 ), sulfur transfer ( Zhang et al, 2019 ), halogen transfer ( Chai et al, 2016 ; Zhang and Cheng, 2017 ), etc. Mastering these specific rearrangement transfer reactions can help to elucidate the structural information of compounds, enrich the content of gas-phase ion chemistry, and also help to discover new pathways of drug metabolism.…”

Section: Introductionmentioning

confidence: 99%

Hydroxyl transfer versus cyclization reaction in the gas phase: Sequential loss of NH3 and CH2CO from protonated phenylalanine derivatives

Zheng

Zhang²,

Cheng³

et al. 2023

Front. Chem.

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Collisional activation of protonated phenylalanine derivatives deamination products leads to hydroxyl skeletal rearrangement versus cyclization reaction, and to form hydroxylbenzyl cation via elimination of CH2CO. To better clarify this unusual fragmentation reaction, accurate mass measurements experiments, native isotope experiments, multiple-stage mass spectrometry experiments, different substituents experiments, and density functional theory (DFT) calculations were carried out to investigate the dissociation mechanistic pathways of protonated phenylalanine derivatives deamination products. In route 1, a three-membered ring-opening reaction and a 1,3-hydroxyl transfer (from the carbonyl carbon atom to the interposition carbon atom of carbonyl) occurs to form 3-hydroxy-1-oxo-3-phenylpropan-1-ylium, followed by dissociation to lose CH2CO to give hydroxy (phenyl)methylium. In route 2, a successive cyclization rearrangement reaction and proton transfer occur to form a 2-hydroxylphenylpropionyl cation or protonated 2-hydroxy-4H-benzopyran, followed by dissociation to lose CH2CO or CH≡COH to give 2-hydroxylbenzyl cation. In route 3, a successive hydroxyl transfer (from the carbonyl carbon atom to the ortho carbon atom on benzene) and two stepwise proton transfer (1,2-proton transfer to the ipso-carbon atom of the phenyl ring followed by 1,3-proton transfer to the ortho carbon atom of carbonyl) occurs to form a 2-hydroxylphenylpropionyl cation, which subsequently dissociates to form 2-hydroxylbenzyl cation by elimination of CH2CO. DFT calculations suggested that route 1 was more favorable than route 2 and route 3 from a thermodynamic point of view.

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“…To obtain insights into the mechanism of lactate fragmentation, we carried out theoretical calculations at the B3LYP/6-31 G(d) level of theory to quantitatively describe the energy requirements of these reactions 32 – 34 and a schematic potential energy surface is illustrated in Fig. 6 .…”

Section: Resultsmentioning

confidence: 99%

Quantification of lactate from various metabolic pathways and quantification issues of lactate isotopologues and isotopmers

Zhang

Guo

Jiang

et al. 2017

Sci Rep

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13C-labeled glucose combined with chromatography and mass spectrometry enables us to decipher the percentage of lactate generated from various metabolic pathways. We showed that lactate derived from glycolysis, pentose phosphate pathway, Krebs cycle, and other sources accounted for 82–90%, 6.0–11%, 0.67–1.8% and 1.5–7.9%, respectively, depending on different types of cells. When using glucose isotopomers ([1-13C]-, [3-13C]-, [4-13C]-, and [6-13C]glucose) or isotopologues ([1,2-13C2]- and [1,2,3-13C3]glucose) for tracing, the ratio of lactate derived from glucose carbon 1, 2, 3 over 4, 5, 6 via glycolysis varied significantly, ranging from 1.6 (traced with [1,2-13C2]glucose) to 0.85 (traced with [6-13C]glucose), but the theoretical ratio should be 1. The odd results might be caused by intramolecular 13C, which may significantly affect lactate fragmentation under tandem mass spectrometry condition, leading to erroneous quantification. Indeed, the fragmentation efficiency of [U-13C]lactate, [2,3-13C]lactate, and [3-13C]lactate were 1.4, 1.5 and 1.2 folds higher than lactate, respectively, but [1-13C]lactate was similar to lactate, suggesting that carbon-13 at different positions could differentially influence lactate fragmentation. This observed phenomenon was inconsistent with the data based on theoretical calculation, according to which activation energies for all lactate isotopomers and isotopologues are nearly identical. The inconsistency suggested a need for further investigation. Our study suggests that calibration is required for quantifying metabolite isotopolugues and isotopomers.

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Dissociation of protonated N‐(3‐phenyl‐2H‐chromen‐2‐ylidene)‐ benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer

Abstract: For the substituted sulfonamides, the presence of electron-donating groups (R(2) -) at the C-ring effectively facilitates the reaction channel of cyclization reaction, whereas that of electron-withdrawing groups inhibits this pathway.

Cited by 7 publications

References 44 publications

Collision‐induced dissociation of phenethylamides: role of ion‐neutral complexes

Collision‐induced dissociation of phenethylamides: role of ion‐neutral complexes

Hydroxyl transfer versus cyclization reaction in the gas phase: Sequential loss of NH3 and CH2CO from protonated phenylalanine derivatives

Quantification of lactate from various metabolic pathways and quantification issues of lactate isotopologues and isotopmers

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