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Title: Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum)

Abstract

Stereoisomers of 5-(2-allylsulfinyl)-3,4-dimethylthiolane-2-ol, a family of 3,4-dimethylthiolanes of formula C 9H 16O 2S 2 we name ajothiolanes, were isolated from garlic (Allium sativum) macerates and characterized by a variety of analytical and spectroscopic techniques, including ultraperformance liquid chromatography (UPLC), direct analysis in real time-mass spectrometry (DART-MS), and liquid chromatography–tandem mass spectrometry (LC-MS/MS). Ajothiolanes were found to be spectroscopically identical to a family of previously described compounds named garlicnins B 1–4 (C 9H 16O 2S 2), whose structures we demonstrate have been misassigned. 2D 13C– 13C NMR incredible natural abundance double quantum transfer experiments (INADEQUATE) were used to disprove the claim of nine contiguous carbons in these compounds, while X-ray absorption spectroscopy (XAS) along with computational modeling was used to disprove the claim that these compounds were thiolanesulfenic acids. On the basis of the similarity of their NMR spectra to those of the ajothiolanes, we propose that the structures of previously described, biologically active onionins A 1–3 (C 9H 16O 2S 2), from extracts of onion (Allium cepa) and Allium fistulosum, and garlicnin A (C 12H 20O 2S 4), from garlic extracts, should also be reassigned, in each case as isomeric mixtures of 5-substituted-3,4-dimethylthiolane-2-ols. We conclude that 3,4-dimethylthiolanes may be amore » common motif in Allium chemistry. Finally, we show that another garlic extract component, garlicnin D (C 7H 12O 2S 3), claimed to have an unprecedented structure, is in fact a known compound from garlic with a structure different from that proposed, namely, 2(E)-3-(methylsulfinyl)-2-propenyl 2-propenyl disulfide.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [2];  [2];  [4];  [5];  [2]
  1. State Univ. of New York, Albany, NY (United States). Dept. of Chemistry
  2. Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Geological Sciences
  3. Tokyo Inst. of Technology, Tokyo (Japan). Dept. of Chemistry
  4. NYS Dept. of Agriculture and Markets, Albany, NY (United States). Food Laboratory Division
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Institutes of Health (NIH)
OSTI Identifier:
1490686
Grant/Contract Number:  
AC02-76SF00515; GM57375; 5R01 DC014423-02; P41GM103393; CHE-0744578; CHE-1429329; CHE-1265679
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Agricultural and Food Chemistry
Additional Journal Information:
Journal Volume: 66; Journal Issue: 39; Journal ID: ISSN 0021-8561
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 3,4-dimethylthiolanes; ajothiolane; Allium cepa; Allium fistulosum; Allium sativum; DART-MS; garlic; INADEQUATE NMR; naturally occurring thiolanes; onion; sulfenic acids; thiolane-2-ol; UPLC; X-ray absorption spectroscopy

Citation Formats

Block, Eric, Dethier, Bérénice, Bechand, Benjamin, Cotelesage, Julien J. H., George, Graham N., Goto, Kei, Pickering, Ingrid J., Mendoza Rengifo, Emerita, Sheridan, Robert, Sneeden, Eileen Y., and Vogt, Linda. Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum). United States: N. p., 2018. Web. doi:10.1021/acs.jafc.8b03638.
Block, Eric, Dethier, Bérénice, Bechand, Benjamin, Cotelesage, Julien J. H., George, Graham N., Goto, Kei, Pickering, Ingrid J., Mendoza Rengifo, Emerita, Sheridan, Robert, Sneeden, Eileen Y., & Vogt, Linda. Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum). United States. doi:10.1021/acs.jafc.8b03638.
Block, Eric, Dethier, Bérénice, Bechand, Benjamin, Cotelesage, Julien J. H., George, Graham N., Goto, Kei, Pickering, Ingrid J., Mendoza Rengifo, Emerita, Sheridan, Robert, Sneeden, Eileen Y., and Vogt, Linda. Sun . "Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum)". United States. doi:10.1021/acs.jafc.8b03638. https://www.osti.gov/servlets/purl/1490686.
@article{osti_1490686,
title = {Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum)},
author = {Block, Eric and Dethier, Bérénice and Bechand, Benjamin and Cotelesage, Julien J. H. and George, Graham N. and Goto, Kei and Pickering, Ingrid J. and Mendoza Rengifo, Emerita and Sheridan, Robert and Sneeden, Eileen Y. and Vogt, Linda},
abstractNote = {Stereoisomers of 5-(2-allylsulfinyl)-3,4-dimethylthiolane-2-ol, a family of 3,4-dimethylthiolanes of formula C9H16O2S2 we name ajothiolanes, were isolated from garlic (Allium sativum) macerates and characterized by a variety of analytical and spectroscopic techniques, including ultraperformance liquid chromatography (UPLC), direct analysis in real time-mass spectrometry (DART-MS), and liquid chromatography–tandem mass spectrometry (LC-MS/MS). Ajothiolanes were found to be spectroscopically identical to a family of previously described compounds named garlicnins B1–4 (C9H16O2S2), whose structures we demonstrate have been misassigned. 2D 13C–13C NMR incredible natural abundance double quantum transfer experiments (INADEQUATE) were used to disprove the claim of nine contiguous carbons in these compounds, while X-ray absorption spectroscopy (XAS) along with computational modeling was used to disprove the claim that these compounds were thiolanesulfenic acids. On the basis of the similarity of their NMR spectra to those of the ajothiolanes, we propose that the structures of previously described, biologically active onionins A1–3 (C9H16O2S2), from extracts of onion (Allium cepa) and Allium fistulosum, and garlicnin A (C12H20O2S4), from garlic extracts, should also be reassigned, in each case as isomeric mixtures of 5-substituted-3,4-dimethylthiolane-2-ols. We conclude that 3,4-dimethylthiolanes may be a common motif in Allium chemistry. Finally, we show that another garlic extract component, garlicnin D (C7H12O2S3), claimed to have an unprecedented structure, is in fact a known compound from garlic with a structure different from that proposed, namely, 2(E)-3-(methylsulfinyl)-2-propenyl 2-propenyl disulfide.},
doi = {10.1021/acs.jafc.8b03638},
journal = {Journal of Agricultural and Food Chemistry},
number = 39,
volume = 66,
place = {United States},
year = {2018},
month = {9}
}

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