Retro‐Diels‐Alder reaction in mass spectrometry

Tureček, František; Hanuš, V.

doi:10.1002/mas.1280030104

Cited by 101 publications

(53 citation statements)

References 280 publications

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“…Since the diene and olefinic parts of the protonated molecule are linked by more than two bonds, the RDA cleavage of the cyclohexene ring does not lead directly to fragmentation and an isomerized ion is formed instead. The latter may further decompose by a simple bond dissociation or rearrangement, but the overall fragmentation may be activated by the RDA cleavage [44]. The product ions produced all contain the dienophilic end of the molecule with the cyclic imine remaining intact.…”

Section: Discussionmentioning

confidence: 98%

Structural study of spirolide marine toxins by mass spectrometry

Sleno

Windust

Volmer

2004

Analytical and Bioanalytical Chemistry

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A novel group of toxins, the spirolides, has been investigated by several mass spectrometric (MS) methods to enable structure elucidation and metabolite identification. These macrocyclic compounds, produced by the dinoflagellate Alexandrium ostenfeldii, are a new class of marine phycotoxin with characteristic spiro-linked tricyclic ether and imine moieties. A crude phytoplankton extract has been shown to contain known spirolides and several unknown compounds, present at low yet significant levels. This study has focused on mass spectrometric characterization of the main component of this extract, 13-desmethyl spirolide C. Collision-induced dissociation (CID) spectra were collected on triple-quadrupole and quadrupole linear ion-trap instruments. High-resolution Fourier-transform ion cyclotron resonance MS data revealed the accurate masses of the protonated molecule and the product ions formed by infrared multiphoton dissociation. A fragmentation scheme for this toxin has been proposed to explain the formation of the collision-induced fragments. Charge-remote fragmentations dominate the CID spectra, because there is only one predominantly basic site in this molecule, and prove to be structurally informative. Extensive MS characterization of 13-desmethyl spirolide C will undoubtedly be useful in the characterization of known and unknown spirolides and other related compounds.

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Section: Discussionmentioning

confidence: 98%

Structural study of spirolide marine toxins by mass spectrometry

Sleno

Windust

Volmer

2004

Analytical and Bioanalytical Chemistry

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“…During the course of our investigations on the homo-and heterocyclic fullerene cycloadducts, we have observed that the molecular odd-electron ions generated under ESI conditions and negative mode of detection from substituted isoxazolinofullerenes [25] . On the other hand, the retro-Diels-Alder reaction (RDA) is a wellknown process, which can be generated in a mass spectrometer [26][27][28], and is one of the most investigated spectrometric process in the fullerene chemistry [29][30][31]. A RDA process is observed when substituted tetrahydroquinazolinofullerenes undergo a fragmentation forming as the only product ion the [60]fullerene [32].…”

Section: Introductionmentioning

confidence: 99%

Mass Spectrometry Studies of the Retro-Cycloaddition Reaction of Pyrrolidino and 2-Pyrazolinofullerene Derivatives Under Negative ESI Conditions

Delgado

Filippone

Martín‐Domenech

et al. 2011

J. Am. Soc. Mass Spectrom.

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Substituted pyrrolidino-and 3-alkyl-2-pyrazolinofullerenes ionize under ESI and MALDI mass spectrometry conditions and negative mode of detection undergoing mass spectral fragmentations, which can be easily correlated with the reported results for the thermal and electrochemical retro-cycloaddition reactions of these compounds. 2-Pyrazolinofullerenes lead directly to a [60] fullerene product ion formed through a retro-cycloaddition process regardless of the substituents attached at the carbon and nitrogen atoms of the heterocyclic ring. These results are different from whose reported for the thermal and electrochemical processes. In contrast, pyrrolidinofullerenes undergo different fragmentative reactions depending upon the substituents (hydrogen, alkyl, or acyl) attached at the nitrogen atom of the heterocyclic ring leading eventually to the pristine C 60 in the last step of the fragmentation pathway.

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“…Comparison of all data mentioned above suggests that in the case of compounds 10a-f methylene group of pyran ring is the most likely source of a proton during an initial [1,4]-H shift step of the molecular ion. Examination of molecular models shows that such proton shift is geometrically possible.…”

Section: Fragmentation Reactions Starting Within a Succinimide Ringmentioning

confidence: 93%

“…Moreover, the KER data suggest that the skeletal rearrangement must take place before the formation of [M − PhNH 2 ] • + ion. Most likely the process starts with C-3-N-2 bond cleavage and is followed by a [1,4]-H shift from the methylene group of pyran ring to the N-2 nitrogen atom, that finally leads to the distonic ion 17 (Scheme 6). Analysis of the daughter ion mass spectra presented in Fig.…”

Section: Fragmentation Reactions Starting Within a Succinimide Ringmentioning

confidence: 99%

“…This result seemed to be important, especially due to the fact that hitherto there has been little instances towards RDA processes of tetrahydropyran-type derivatives in the literature. It is well known that RDA fragmentation is common for tetrahydronaphtalenes and their 1-S and 1-N heteroanalogs [1,4,5]. Recently a paper by Martin and co-workers provided some examples of retro Diels-Alder reaction in reference to chromene-type derivatives under EI, CA and ESI conditions [6].…”

Section: Introductionmentioning

confidence: 97%

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