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 B_1–4 (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 A_1–3 (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.

中文翻译：

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Ajothiolanes：大蒜3,4-Dimethylthiolane天然产物（大蒜）

5-（2- allylsulfinyl）-3,4- dimethylthiolane -2-醇，一个家庭的式3,4- dimethylthiolanes的立体异构体Ç ₉ ħ ₁₆ ö ₂ š _2个我们名ajothiolanes，从大蒜分离（大蒜）浸软并通过多种分析和光谱技术进行表征，包括超高效液相色谱（UPLC），实时质谱直接分析（DART-MS）和液相色谱-串联质谱（LC-MS / MS）。已发现硫唑烷在光谱上与先前描述的名为大蒜​​素B _1–4（C ₉ H ₁₆ O ₂ S _2的化合物）相同），我们展示的结构已被错误分配。2D ¹³ C- ¹³ C NMR我ncredible Ñ atural一个bundance d oubl ËQUA NTUM吨转让（BOT）ë xperiments（INADEQUATE）被用来反驳的这些化合物在九个连续的碳原子的权利要求，而X射线吸收光谱（XAS）连同计算模型被用来反驳这些化合物是硫烷磺酸的说法。根据它们的核磁共振光谱与阿育硫烷的核磁共振光谱的相似性，我们建议采用先前描述的具有生物活性的洋葱素A _1–3（C ₉ħ ₁₆ ö ₂ s ^ ₂），从洋葱（提取物洋葱）和大葱，和garlicnin A（C ₁₂ H ^ ₂₀ ö ₂ s ^ ₄），从大蒜提取物，也应该被重新分配，在每一情况下作为异构体混合物5-取代的3，4-二甲基硫杂环戊烷-2-醇。我们得出结论，3,4-二甲基硫杂环戊烷可能是葱属化学中的常见基序。最后，我们显示了另一种大蒜提取物成分大蒜素D（C ₇ H ₁₂ O ₂ S ₃（据称具有空前的结构）实际上是大蒜中已知的化合物，其结构不同于所提出的结构，即2（E）-3-（甲基亚磺酰基）-2-丙烯基2-丙烯基二硫化物。