1,6-dideoxy-1,6-epithio-β-D-glucopyranose | 4984-68-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻庚烷
• 英文名称: 1,6-dideoxy-1,6-epithio-β-D-glucopyranose
• 英文别名: 1,6-Anhydro-6-thio-β-D-glucopyranose；1,6-anhydro-1-thio-β-D-glucopyranose；1,6-thioanhydro-D-glucopyranose；thiolevoglucosan；1,6-Anhydro-1,6-sulfid-β-D-glucopyranose；(1S,2S,3S,4R,5S)-8-oxa-6-thiabicyclo[3.2.1]octane-2,3,4-triol
• CAS: 4984-68-3
• 化学式: C₆H₁₀O₄S
• 分子量: 178.209
• InChiKey: TYDHICSSLDZTOS-DVKNGEFBSA-N

物化性质

• 熔点：
  165-180 °C (decomp)(Solv: ethanol (64-17-5))
• 沸点：
  403.7±45.0 °C(Predicted)
• 密度：
  1.706±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  95.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,6-dideoxy-1,6-epithio-β-D-glucopyranose 在 4-二甲氨基吡啶 、 三氟乙酸2,2,2-三氟乙酯 、 4-羧基苯磺叠氮 、 silver nitrate 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 生成 3-O-(diazoacetyl)-2,4-O-(di-tert-butylsilane-1,1-diyl)-1,6-thioanhydro-D-glucopyranose
  参考文献：
  名称：

  1-脱氧-1-硫-1,6-脱水糖与α-重氮化合物的分子间和分子内反应：通过光化学内酯重排合成塔格毒素核心†

  摘要：

  已经提出了由金属卡宾介导并通过硫酰化物的中间进行的1-脱氧-1-硫代-1,6-脱水糖的单碳环膨胀，作为合成塔格毒素框架的途径。此类硫代脱水糖与重氮酸酯的分子间反应提供了一系列源自最初形成的叶立德的不希望有的产物，而使用分子内过程会生成稳定的叶立德，这些叶立德可以通过光-史蒂文斯重排而转化为塔格毒素框架。使用密度泛函理论的计算研究表明，光化学重排可能通过均相-重组途径进行。

  DOI：

  10.1039/c2ob26308d
• 作为产物：
  描述：

  2,3,4-tri-O-acetyl-1,6-dideoxy-1,6-epithio-β-D-glucopyranose 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以99%的产率得到1,6-dideoxy-1,6-epithio-β-D-glucopyranose
  参考文献：
  名称：

  1,6-Anhydro-1-thio-β-D-glucopyranose (Thiolevoglucosan) and the Corresponding Sulfoxides and Sulfone

  摘要：

  将1,2,3,4-四O-乙酰基-6-O-对甲苯磺酰基-β-D-葡萄糖吡喃糖（3）转化为2,3,4-三O-乙酰基-1-硫-6-O-对甲苯磺酰基-β-D-葡萄糖吡喃糖（6），通过中间体糖溴化物4和S-硫代脲盐5。用甲氧基钠处理化合物6得到1,6-脱水-1-硫-β-D-葡萄糖吡喃糖（硫代乙基葡萄糖2a）。异构的亚砜7和8通过过氧化氢或3-氯过氧苯甲酸选择性氧化硫代乙基葡萄糖2a制备。新化合物的结构通过¹H和¹³C核磁共振或X射线分析确认；讨论了亚砜基和磺酰基的磁各向异性。

  DOI：

  10.1135/cccc20060311

文献信息

• 1,6-Anhydro-1-thio-β-D-glucopyranose (Thiolevoglucosan) and the Corresponding Sulfoxides and Sulfone
  作者：Miloš Buděšínský、Jana Poláková、Michaela Hamerníková、Ivana Císařová、Tomáš Trnka、Miloslav Černý

  DOI：10.1135/cccc20060311

  日期：——

  Starting 1,2,3,4-tetra-O-acetyl-6-O-tosyl-β-D-glucopyranose (3) was converted into 2,3,4-tri-O-acetyl-1-thio-6-O-tosyl-β-D-glucopyranose (6) via intermediate glycosyl bromide 4 and S-thiouronium salt 5. Treatment of compound 6 with sodium methoxide gave 1,6-anhydro-1-thio-β-D-glucopyranose (thiolevoglucosan 2a). The isomeric sulfoxides 7 and 8 were prepared by selective oxidation of thiolevoglucosan 2a with hydrogen peroxide or 3-chloroperoxybenzoic acid. The structure of new compounds was confirmed by ¹H and ¹³C NMR spectroscopy or by X-ray analysis; magnetic anisotropy of the sulfinyl and sulfonyl group has been discussed.

  将1,2,3,4-四O-乙酰基-6-O-对甲苯磺酰基-β-D-葡萄糖吡喃糖（3）转化为2,3,4-三O-乙酰基-1-硫-6-O-对甲苯磺酰基-β-D-葡萄糖吡喃糖（6），通过中间体糖溴化物4和S-硫代脲盐5。用甲氧基钠处理化合物6得到1,6-脱水-1-硫-β-D-葡萄糖吡喃糖（硫代乙基葡萄糖2a）。异构的亚砜7和8通过过氧化氢或3-氯过氧苯甲酸选择性氧化硫代乙基葡萄糖2a制备。新化合物的结构通过¹H和¹³C核磁共振或X射线分析确认；讨论了亚砜基和磺酰基的磁各向异性。
• Biochemical Studies on Thiosugars. IV. Synthesis of 1, 6-Anhydro-1, 6-sulfide-β-D-glucopyranose (Thiolevoglucosan) and 6-Deoxy-6-mercapto-1-thio-D-glucose.
  作者：Masuo Akagi、Setsuzo Tejima、Masanobu Haga

  DOI：10.1248/cpb.11.58

  日期：——

  1, 6-Anhydro-1, 6-sulfide-2, 3, 4-tri-O-acetyl-β-D-glucopyranose was synthesized by alkali-degradation and successive acetylation of 6-O-tosyl-2, 3, 4-tri-O-acetyl-β-D-glucopyranosyl ethylxanthate and 6-O-tosyl-1-deoxy-1-acethylthio-2, 3, 4-tri-O-acetyl-β-D-glucopyranose, which were prepared from 6-O-tosyl-2, 3, 4-tri-O-acetyl-α-D-glucopyranosyl bromide with potassium ethylxanthate and potassium thiolacetate respectively. On desulfurization of 1, 6-anhydro-1, 6-sulfide-2, 3, 4-tri-O-acetyl-β-D-glucopyranose with Raney nickel, 6-deoxy-1, 5-anhydro-D-sorbitol tracetate was obtained. 1, 6-Dideoxy-1, 6-diacetylthio-2, 3, 4-tri-O-acetyl-β-D-glucopyranose was prepared from 6-deoxy-6-acetylthio-2, 3, 4-tri-O-acetyl-α-D-glucopyranosyl bromide, which was synthesized from 6-deoxy-6-acetylthio-1, 2, 3, 4-tetra-O-acetyl-β-D-glucopyranose, and potassium thiolacetate. The structure was also confirmed by desulfurization with Raney nickel according to give 6-deoxy-1, 5-anhydro-D-sorbitol.

  6-O-甲苯磺酰基-2, 3, 4经碱解、连续乙酰化合成1, 6-脱水-1, 6-硫化物-2, 3, 4-三-O-乙酰基-β-D-吡喃葡萄糖-三-O-乙酰基-β-D-吡喃葡萄糖基乙基黄原酸酯和 6-O-甲苯磺酰基-1-脱氧-1-乙酰硫基-2,3,4-三-O-乙酰基-β-D-吡喃葡萄糖，制备自6-O-甲苯磺酰基-2,3,4-三-O-乙酰基-α-D-吡喃葡萄糖基溴分别与乙基黄原酸钾和硫代乙酸钾反应。 6-脱氧-1, 5-脱水-D-山梨糖醇踪迹酸雷尼镍对1, 6-脱水-1, 6-硫化物-2, 3, 4-三-O-乙酰基-β-D-吡喃葡萄糖的脱硫研究获得了。 1, 6-二脱氧-1, 6-二乙酰硫基-2, 3, 4-三-O-乙酰基-β-D-吡喃葡萄糖由 6-脱氧-6-乙酰硫基-2, 3, 4-三-O-制备乙酰-α-D-吡喃葡萄糖基溴，由6-脱氧-6-乙酰硫基-1,2,3,4-四-O-乙酰基-β-D-吡喃葡萄糖和硫代乙酸钾合成。经雷尼镍脱硫也证实了结构，得到6-脱氧-1,5-脱水-D-山梨醇。
• Synthesis of the Tagetitoxin Core via Photo-Stevens Rearrangement
  作者：Anne J. Price Mortimer、Abil E. Aliev、Derek A. Tocher、Michael J. Porter

  DOI：10.1021/ol802297h

  日期：2008.12.4

  The core structure of the RNA polymerase inhibitor tagetitoxin has been synthesized by one-carbon ring expansion of bridged bicyclic monothioacetals. The key steps are intramolecular ylide formation by reaction between the sulfur atom and a pendant diazoester, followed by an efficient photochemical 1,2-rearrangement to give the desired 9-oxa-3-thiabicyclo[3.3.1]nonane ring system.

  RNA聚合酶抑制剂tagetitoxin的核心结构已通过桥联的双环单硫缩醛的一碳环扩展合成。关键步骤是通过硫原子与侧基重氮酸酯之间的反应形成分子内叶立德，然后进行有效的光化学1,2-重排，得到所需的9-氧杂-3-噻二环[3.3.1]壬烷环系统。
• 1,6-epithio- and 1,6-episeleno-β-d-glucopyranose: Useful adjuncts in the synthesis of 6-deoxy-β-d-glucopyranosides
  作者：Robert V Stick、D Matthew、G Tilbrook、Spencer J Williams

  DOI：10.1016/s0040-4039(97)00458-9

  日期：1997.4

  The treatment of derivatives of 1,6-epithio- and 1,6-episeleno-beta-D-glucopyranose with various carbohydrate alcohols in the presence of N-iodosuccinimide/triflic acid gives rise to di sulfides and diselenides, respectively, which may be transformed to the desired 6-deoxy-beta-D-glucopyranosides. (C) 1997 Elsevier Science Ltd.
• Inter- and intramolecular reactions of 1-deoxy-1-thio-1,6-anhydrosugars with α-diazoesters: synthesis of the tagetitoxin core by photochemical ylide rearrangement
  作者：Anne J. Price Mortimer、Julien R. H. Plet、Oluwafunsho A. Obasanjo、Nikolas Kaltsoyannis、Michael J. Porter

  DOI：10.1039/c2ob26308d

  日期：——

  intermediacy of sulfur ylides, has been proposed as a route for the synthesis of the tagetitoxin skeleton. Intermolecular reactions of such thioanhydrosugars with diazoesters afford a range of undesired products derived from the initially formed ylide, whereas use of an intramolecular process generates stable ylides which can be converted to the tagetitoxin skeleton by photo-Stevens rearrangement. Computational

  已经提出了由金属卡宾介导并通过硫酰化物的中间进行的1-脱氧-1-硫代-1,6-脱水糖的单碳环膨胀，作为合成塔格毒素框架的途径。此类硫代脱水糖与重氮酸酯的分子间反应提供了一系列源自最初形成的叶立德的不希望有的产物，而使用分子内过程会生成稳定的叶立德，这些叶立德可以通过光-史蒂文斯重排而转化为塔格毒素框架。使用密度泛函理论的计算研究表明，光化学重排可能通过均相-重组途径进行。