2,3,4-tri-O-acetyl-1-S-acetyl-1-thio-β-D-xylopyranose | 6739-54-4

• 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: 2,3,4-tri-O-acetyl-1-S-acetyl-1-thio-β-D-xylopyranose
• 英文别名: per-O-acetyl 1-S-acetyl-1-thio-β-D-xylopyranose；[(3R,4S,5R,6S)-4,5-diacetyloxy-6-acetylsulfanyloxan-3-yl] acetate
• CAS: 6739-54-4
• 化学式: C₁₃H₁₈O₈S
• 分子量: 334.347
• InChiKey: IUYWMJNQCVNFEQ-XQHKEYJVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  131
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2,3,4-tri-O-acetyl-1-S-acetyl-1-thio-β-D-xylopyranose 在 L-1,4-二硫代苏糖醇 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 1.0h， 以96%的产率得到2,3,4-tri-O-acetyl-1-thio-β-D-xylopyranose
  参考文献：
  名称：

  受天然化学连接启发的选择性S-脱乙酰化：糖基硫醇和药物巯基类似物的实用合成

  摘要：

  通过在温和的碱性条件下进行简单的硫代酯基转移，即可实现高效的选择性S-脱乙酰基作用。

  DOI：

  10.1039/c5gc00084j
• 作为产物：
  描述：

  2,3,4-tri-O-acetyl-D-xylopyranosyl bromide 在 potassium thioacetate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以60 %的产率得到2,3,4-tri-O-acetyl-1-S-acetyl-1-thio-β-D-xylopyranose
  参考文献：
  名称：

  一种潜在的毛发生长刺激剂香花苷的全合成：一种通过一锅 S- 和 O-糖苷键形成的简便合成方法

  摘要：

  首次全合成花斑苷 ( 1 )，对人毛囊真皮乳头细胞表现出强大的增殖活性，从邻氨基苯甲酸开始，经过七个步骤实现了克级总产率 43% ( 11 )。该合成策略采用一锅法，涉及通过亲核取代反应和烯醇-葡萄糖基化形成硫代葡萄糖苷键，以构建1的S- , O-双锁链苷结构。此外，一锅反应对d-葡萄糖以外的几种糖供体表现出广泛的底物适应性，从而以约 84% 的产率提供S , O-双糖苷中间体。

  DOI：

  10.1021/acs.jnatprod.3c00815

文献信息

• Practical synthesis of latent disarmed S-2-(2-propylthio)benzyl glycosides for interrupted Pummerer reaction mediated glycosylation
  作者：Yang Xu、Qian Zhang、Ying Xiao、Pinru Wu、Wei Chen、Zejin Song、Xiong Xiao、Lingkui Meng、Jing Zeng、Qian Wan

  DOI：10.1016/j.tetlet.2017.05.014

  日期：2017.6

  Practical synthetic methods to latent disarmed S-2-(2-propylthio)benzyl (SPTB) glycosides for interrupted Pummerer reaction mediated glycosylation have been discovered. Among them, both coupling reaction of PTB-Cl with glycosyl thiols and BF3·OEt2 promoted reaction of peracylated glycosides with PTB-SH produced peracylated SPTB glycosides in large scales and with high efficiency.

  已经发现了潜在的解除武装的S -2-（2-丙硫基）苄基（SPTB）糖苷用于中断的Pummerer反应介导的糖基化的实用合成方法。其中，PTB-Cl与糖基硫醇的偶联反应和BF 3 ·OEt 2均促进了过酰化的糖苷与PTB-SH的反应，从而大规模，高效地生产了过酰化的SPTB糖苷。
• Stereoselective synthesis of 1,2-trans-1-thioglycoses using aluminium chloride: Evidence for 1,2-cis-1-chloroglycopyranosylperacetates as the actual reaction intermediates
  作者：B. Rajanikanth、R. Seshadri

  DOI：10.1016/s0040-4039(00)96105-7

  日期：1987.1

  Synthesis of 1,2-trans-1-thioglycosylacetates has been achieved in excellent yields from corresponding 1,2-trans-glycosylacetates using aluminium chloride via 1,2-cis-1-chloroglycopyranosylacetates with retention of configuration.

  使用氯化铝，通过1,2-顺式-1-氯代葡糖基葡糖基乙酸酯从相应的1,2-反式-糖基乙酸酯以优异的产率实现了1,2-反式-1-硫代糖基乙酸酯的合成，并保持了构型。
• Improved Synthesis of 1‐Glycosyl Thioacetates and Its Application in the Synthesis of Thioglucoside Gliflozin Analogues
  作者：Guang‐Jing Feng、Shuang‐Shuang Wang、Jian Lv、Tao Luo、Yuzhou Wu、Hai Dong

  DOI：10.1002/ejoc.202100357

  日期：2021.6.7

  We reported relative green synthesis of 1-thioglycosides by straightforward reaction of per-O-acetylated glycoses with KSAc in EtOAc. Furthermore, the highly efficient method to synthesize per-O-acetylated glycosyl disulfide and glycosyl 1-thiol were developed. Based on this, the synthesis of auranofin was improved and two thioglucoside gliflozin analogues (possible SGLT inhibitors) were efficiently

  我们报道的1-硫代糖苷相对绿色合成由per-的直接的反应Ó于EtOAc -acetylated葡糖与KSAc。此外，还开发了合成过氧乙酰化糖基二硫化物和糖基 1-硫醇的高效方法。在此基础上，金诺芬的合成得到改进，并以高产率高效合成了两种硫代葡萄糖苷格列净类似物（可能是 SGLT 抑制剂）。
• Modular Synthesis of Aryl Thio/Selenoglycosides via the Catellani Strategy
  作者：Ya-Nan Ding、Yan-Chong Huang、Wei-Yu Shi、Nian Zheng、Cui-Tian Wang、Xi Chen、Yang An、Zhe Zhang、Yong-Min Liang

  DOI：10.1021/acs.orglett.1c01723

  日期：2021.8.6

  We described a novel palladium-catalyzed domino procedure for the preparation of (hetero)aryl thio/selenoglycosides. Readily available (hetero)aryl iodides and easily accessible 1-thiosugars/1-selenosugars are utilized as the substrates. Meanwhile, 10 types of sugars are quite compatible with this reaction with good regio- and stereoselectivity, high efficiency, and broad applicability (up to 89%,

  我们描述了一种用于制备（杂）芳基硫代/硒糖苷的新型钯催化多米诺骨牌程序。容易获得的（杂）芳基碘化物和容易获得的 1-硫糖/1-硒糖被用作底物。同时，10种糖类与该反应相容，具有良好的区域选择性和立体选择性、高效率和广泛的适用性（高达89%，53例）。该方法能够直接形成（杂）芳基硫代/硒糖苷的 C(sp 2 )–S/Se 键。
• Family of thiomercuric derivatives of sugars: Synthesis, fungicidal/herbicidal activity, and application to the X‐ray structure determination of the corresponding enzymes
  作者：Valery Belakhov、Evgenia Dor、Joseph Hershenhorn、Mark Botoshansky、Tsafrir Bravman、Mirit Kolog、Yuval Shoham、Gil Shoham、Timor Baasov

  DOI：10.1560/e8dm-02pk-dl0v-u7fr

  日期：2000.12

  A series of thiomercuric derivatives of mono‐ and disaccharides 1–7, in which methylmercury or phenylmercury is covalently attached to anomeric thioglycosides, were synthesized for structure—function studies of glycosidases. Thiomethylmercuryl xylobiosides 5 and 6 were found to inhibit intracellular xylanase‐T6 in a competitive manner, with K_i values of 0.35 mM and 0.01 mM, respectively. These inhibitors have been co‐crystallized with the enzyme and are being used for X‐ray analysis. 1‐(Thiomethylmercuric)‐ß‐D‐xyloside (3) affords crystals belonging to the orthorhombic space group P2₁2₁2₁ and at 293(2) K: a = 6.7510(2), b = 9.7140(2), c = 29.4770(9) Å, V = 1933.08(9) Å, Z = 8, R(F²) = 0.0329, and R_w(F²) = 0.0626. There are two molecules (A and B) in the asymmetric unit, and each one shows an almost linear S–Hg–C arrangement. Biological tests on 1–7 indicated that they exhibit potent fungicidal and herbicidal activities.

  摘要 合成了一系列单糖和二糖的硫代汞衍生物1-7，其中甲基汞或苯基汞共价连接到硫代糖苷的异构体上，用于糖苷酶的结构-功能研究。研究发现，硫代甲基汞木糖苷 5 和 6 能以竞争方式抑制细胞内的木聚糖酶-T6，其 Ki 值分别为 0.35 mM 和 0.01 mM。这些抑制剂已与该酶共同结晶，目前正用于 X 射线分析。1-(Thiomethylmercuric)-ß-D-xyloside (3) 结晶属于正交空间群 P212121，在 293(2) K 时：a = 6.7510(2)，b = 9.7140(2)，c = 29.4770(9)埃，V = 1933.08(9)埃，Z = 8，R(F2) = 0.0329，Rw(F2) = 0.0626。不对称单元中有两个分子（A 和 B），每个分子几乎都呈线性 S-Hg-C 排列。对 1-7 进行的生物测试表明，它们具有很强的杀真菌和除草活性。