tetra-O-acetyl-2-S-acetyl-2-thio-β-D-glucopyranose | 627509-60-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tetra-O-acetyl-2-S-acetyl-2-thio-β-D-glucopyranose
• 英文别名: 1,3,4,6-tetra-O-acetyl-2-S-acetyl-2-thio-β-D-glucopyranose；1,2,3,4,6-penta-O,S,O,O,O-acetyl-2-thio-β-D-glucopyranose；[(2R,3R,4S,5R,6S)-3,4,6-triacetyloxy-5-acetylsulfanyloxan-2-yl]methyl acetate
• CAS: 627509-60-8
• 化学式: C₁₆H₂₂O₁₀S
• 分子量: 406.411
• InChiKey: DPTDBGADTWPWQJ-IBEHDNSVSA-N

物化性质

• 熔点：
  117.5-118.5 °C
• 沸点：
  485.0±45.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  157
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  tetra-O-acetyl-2-S-acetyl-2-thio-β-D-glucopyranose 在 三氟甲磺酸三甲基硅酯 、 镍 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 1,2:3,4-di-O-isopropylidene-6-O-(3,4,6-tri-O-acetyl-2-deoxy-β-D-arabino-hexopyranosyl)-α-D-galactopyranose
  参考文献：
  名称：

  Glycosylation with 2′-thio-S-acetyl participation

  摘要：

  The reaction of 1,2,3,4,6-penta-O,S,O,O,O-acetyl-2-thio-beta-D-glucopyranose with glycosyl acceptors in the presence of trimethylsilyl triflate leads to the beta-disaccharides exclusively, owing to especially avid anchimeric assistance by the 2-thio-S-acetyl group. Optional reductive removal of -SAc with Ra-Ni gives the corresponding 2'-deoxy-beta-disaccharides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.063
• 作为产物：
  描述：

  甘露糖 在 吡啶 、 2,4,6-三甲基吡啶 、 盐酸 、 氢溴酸 、 碘 、 乙酸酐 、 溶剂黄146 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 为溶剂， 反应 4.08h， 生成 tetra-O-acetyl-2-S-acetyl-2-thio-β-D-glucopyranose
  参考文献：
  名称：

  TFPP-葡萄糖结合物的位置异构体的合成，光物理性质和光动力活性

  摘要：

  本文报道了四（全氟苯基）卟啉（TFPP）-葡萄糖缀合物（1OH，2OH，3OH，4OH和6OH）的位置异构体的“完整集”的合成和表征。为了研究TFPP部分在d-葡萄糖分子上的位置对缀合物的生物学活性的影响，检查了这些缀合物的细胞摄取和光细胞毒性。一种在体外生物评价，结果这些特定的异构体对细胞摄取和细胞毒性比别人更大的影响。TFPP-葡萄糖结合物1OH，3OH和与2OH和6OH取代的异构体相比，发现4OH在几种类型的癌细胞中具有优异的光细胞毒性。

  DOI：

  10.1016/j.bmc.2018.02.031

文献信息

• From glycoside hydrolases to thioglycoligases: the synthesis of thioglycosides
  作者：Robert V. Stick、Keith A. Stubbs

  DOI：10.1016/j.tetasy.2004.12.004

  日期：2005.1

  any thioglycosides––only the products of O-glycosylation were formed. However, thioglycosides were formed when a thioglycoligase was used to mediate the reaction between acceptor and donor. In fact, pyranose acceptors possessing a thiol group at C3, C4 or C6 (but not C2) were all capable of conversion into thioglycosides. Some comment is given regarding the mechanism of the various processes.

  用适当的糖基供体和糖苷水解酶或糖合酶处理各种含活性硫醇基的糖基受体，都不能产生任何硫糖苷，只能形成O-糖基化产物。然而，当使用硫代糖基寡糖酶来介导受体和供体之间的反应时，形成了硫代糖苷。实际上，在C3，C4或C6具有巯基的吡喃糖受体（但没有C2）均能够转化为硫糖苷。给出了有关各种过程机制的一些评论。
• Efficient Preparation of 2‐SAc‐Glycosyl Donors and Investigation of Their Application in the Synthesis of 2‐Deoxyglycosides
  作者：Tao Luo、Qiang Zhang、Yang‐Fan Guo、Zhi‐Chao Pei、Hai Dong

  DOI：10.1002/ejoc.202200533

  日期：2022.7.14

  We have developed efficient strategies for the synthesis of glycosyl donors with 2-thioacetyl (SAc) groups in order to synthesize 2-deoxysugars with absolute α/β configuration.

  我们开发了合成具有 2-硫乙酰 (SAc) 基团的糖基供体的有效策略，以合成具有绝对 α/β 构型的 2-脱氧糖。
• Recent advances in the synthesis of 2-deoxy-glycosides
  作者：Dianjie Hou、Todd L. Lowary

  DOI：10.1016/j.carres.2009.07.013

  日期：2009.10

  Glycosides of 2-deoxy-sugars, monosaccharides in which the hydroxyl group at C-2 is replaced with a hydrogen atom, occur widely in natural products and therefore have been the subject of intense synthetic activity. The report summarizes recent advances in this area, with a particular focus on work published since an earlier review on the topic, in 2000 (Marzabadi, C. H.: Franck, R. W. Tetrahedron 2000, 56, 8385-8417). (C) 2009 Elsevier Ltd. All rights reserved.
• A Biosynthetic Pathway for BE-7585A, a 2-Thiosugar-Containing Angucycline-Type Natural Product
  作者：Eita Sasaki、Yasushi Ogasawara、Hung-wen Liu

  DOI：10.1021/ja1014037

  日期：2010.6.2

  Sulfur is an essential element found ubiquitously in living systems. However, there exist only a few sulfur-containing sugars in nature and their biosyntheses have not been studied. BE-7585A produced by Amycolatopsis orientalis subsp. vinearia BA-07585 has a 2-thiosugar and is a member of the angucycline class of compounds. We report herein the results of our initial efforts to study the biosynthesis of BE-7585A. Spectroscopic analyses verified the structure of BE-7585A, which is closely related to rhodonocardin A. Feeding experiments using C-13-labeled acetate were carried out to confirm that the angucycline core is indeed polyketide-derived. The results indicated an unusual manner of angular tetracyclic ring construction, perhaps via a Baeyer-Villiger type rearrangement. Subsequent cloning and sequencing led to the identification of the bex gene cluster spanning similar to 30 kbp. A total of 28 open reading frames, which are likely involved in BE-7585A formation, were identified in the cluster. In view of the presence of a homologue of a thiazole synthase gene (thiG), bexX, in the bex cluster, the mechanism of sulfur incorporation into the 2-thiosugar moiety could resemble that found in thiamin biosynthesis. A glycosyltransferase homologue, BexG2, was heterologously expressed in Escherichia coli. The purified enzyme successfully catalyzed the coupling of 2-thioglucose 6-phoshate and UDP-glucose to produce 2-thiotrehalose 6-phosphate, which is the precursor of the disaccharide unit in BE-7585A. On the basis of these genetic and biochemical experiments, a biosynthetic pathway for BE-7585A can now be proposed. The combined results set the stage for future biochemical studies of 2-thiosugar biosynthesis and BE-7585A assembly.
• A One-Pot Method for Removal of Thioacetyl Group via Desulfurization under Ultraviolet Light To Synthesize Deoxyglycosides
  作者：Jian-Tao Ge、Lang Zhou、Tao Luo、Jian Lv、Hai Dong

  DOI：10.1021/acs.orglett.9b02033

  日期：2019.8.2

  We herein developed an efficient method for removing thioacetyl to synthesize acylated deoxy glycosides in a one-pot reaction, where the thioacetyl was selectively deacetylated by hydrazine hydrate in DMF within 2-5 min at room temperature, followed by desulfurization under UV light for 1-2 h in the presence of TCEP center dot HCl. The method was then used to synthesize 2-deoxy glycosides with absolute alpha/beta-configuration via stereoselective control of C-2 thioacetate in glycosylation.