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

Journal Article · · Journal of Agricultural and Food Chemistry
 [1];  [1];  [1];  [2];  [2];  [3];  [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)
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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.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Institutes of Health (NIH)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1490686
Journal Information:
Journal of Agricultural and Food Chemistry, Journal Name: Journal of Agricultural and Food Chemistry Journal Issue: 39 Vol. 66; ISSN 0021-8561
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (1)

S-Alk(en)ylcysteine sulfoxides in the genus Allium: proposed biosynthesis, chemical conversion, and bioactivities journal May 2019

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Related Subjects

3
4-dimethylthiolanes
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
59 BASIC BIOLOGICAL SCIENCES
Allium cepa
Allium fistulosum
Allium sativum
DART-MS
INADEQUATE NMR
UPLC
X-ray absorption spectroscopy
ajothiolane
garlic
naturally occurring thiolanes
onion
sulfenic acids
thiolane-2-ol