1,5-anhydro-2,3,4-tri-O-acetyl-5-thio-D-xylitol | 351462-97-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: 1,5-anhydro-2,3,4-tri-O-acetyl-5-thio-D-xylitol
• 英文别名: 2,3,4-tri-O-acetyl-1,5-dideoxy-1,5-thioxylitol；1,5-anhydro-2,3,4-tri-O-acetyl-5-thioxylitol
• CAS: 351462-97-0
• 化学式: C₁₁H₁₆O₆S
• 分子量: 276.31
• InChiKey: IUCXWQFZAKZLEX-URLYPYJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.53
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  78.9
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-2,3,4-tri-O-acetyl-5-thio-D-xylitol 在 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 (3S,4S,5R)-3,4,5-tris(benzyloxy)tetrahydro-2H-thiopyran
  参考文献：
  名称：

  烷基化脱氧野尻霉素和 1,5-Dideoxy-1,5-亚氨基木糖醇类似物的合成：极性侧链修饰、锍和硒杂原子变体、构象分析和作为糖苷酶抑制剂的评估

  摘要：

  报道了 N-烷基化脱氧野尻霉素和具有 D-或 L-赤藓糖醇-3-硫酸酯官能化 N-取代基的 1,5-dideoxy-1,5-亚氨基木糖醇衍生物的合成。所用的烷基化剂是环状硫酸盐衍生物，由此选择性地攻击受阻最小的一级中心处的氮原子，得到所需的铵盐。在水溶液中，这些盐在铵中心的构型不稳定。铵盐的锍和/或硒鎓类似物通过类似反应制备。硫属元素盐是作为非对映异构体的混合物获得的，在某些情况下是可分离的，仅在构型稳定的硫或硒原子的立体化学上有所不同。通过详细的 NMR 实验获得了每种化合物的构型和构象的证据。这些化合物是 salacinol 的六元环类似物，是一种已知的锍盐葡萄糖苷酶抑制剂。对目标化合物对葡糖苷酶葡糖淀粉酶 G2 的酶抑制作用的评估表明，这些化合物要么是无活性的，要么最多只是麦芽糖水解的弱抑制剂。

  DOI：

  10.1021/ja0482076
• 作为产物：
  描述：

  Xylitol 在 吡啶 、 sodium sulfide 、 乙酰溴 作用下， 以 1,4-二氧六环 、 二甲基亚砜 为溶剂， 反应 0.5h， 生成 1,5-anhydro-2,3,4-tri-O-acetyl-5-thio-D-xylitol
  参考文献：
  名称：

  Short and efficient synthesis of polyhydroxylated tetrahydrothiophene, tetrahydrothiopyrane and thiepane from bielectrophilic erythro, threo, xylo, ribo, arabino, manno and gluco α,ω-dibromoalditol derivatives

  摘要：

  Polyhydroxylated tetrahydrothiophene, tetrahydrothiopyrane and thiepane rings have been readily obtained in excellent yields (78-95%) from thioheterocyclisation of the bielectrophilic petacetylated alpha,omega -dibrominated derivatives of tetritols (erythritol (1) and D,L-threitol (4)), pentitols: (xylitol (7), ribitol (10) and D-arabinitol (14)) and hexitols (D-mannitol (17) and D-glucitol (20)), respectively. With 2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol (21) as substrate, the unexpected 2,6-anhydro derivative 25 was obtained. This could be attributed to previous S-= regioselective nucleophilic attack at C-1 position followed by 1,2-transesterification and 2,6-O-heterocyclisation. The preferential attack at C-1 of the D-glucitol derivative 21 subsequently allowed a facile direct synthesis in good yields of 2,3,4,5,6-penta-O-acetyl-1-bromo-1-deoxy-D-glucitol (26), 2,3,4,5-tetra-O-acetyl-6-bromo-6-deoxy-1-thiobutyl-1-deoxy-D-glucitol (28) and 2,3,3,5-tetra-O-acetyl-6-bromo-6-deoxy-1-thiooctyl-1-deoxy-D-glucitol (28). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00442-7

文献信息

• A Mild Pummerer-Like Reaction of Carbohydrate-Based Selenoethers and Thioethers Involving Linear Ozonide Acetates as Putative Intermediates
  作者：Natacha Veerapen、Stephanie. A. Taylor、Charles. J. Walsby、B. Mario Pinto

  DOI：10.1021/ja0557029

  日期：2006.1.1

  carbohydrate-based heterocycles containing selenium and sulfur were investigated. To the best of our knowledge, this is the first report on the Pummerer rearrangement in selenoheterocycles. Ozonization of 1,4-anhydro-D-galactitol or 1,5-anhydroxylitol derivatives containing sulfur or selenium as the ring heteroatom gave unstable intermediates that were attributed to ozonides. These intermediates decomposed upon warming

  研究了含硒和硫的基于碳水化合物的杂环的类 Pummerer 重排。据我们所知，这是关于硒杂环中Pummerer 重排的第一份报告。含硫或硒作为环杂原子的 1,4-脱水-D-半乳糖醇或 1,5-anhydroxylitol 衍生物的臭氧化产生归因于臭氧化物的不稳定中间体。这些中间体在加热时分解，得到硒氧化物或亚砜。值得注意的是，在低温下向臭氧化反应混合物中加入乙酸酐，在升温至环境温度后得到普默勒重排产物。然而，当分离出的硒氧化物或亚砜用乙酸酐处理时，会发生普默勒重排，但亚砜需要更高的反应温度。后一个结果与前一个结果不同，并根据前一种情况下的臭氧乙酸中间体的重排来解释。为了探究重排是通过单线态氧的挤出进行异裂还是通过自由基的产生进行均裂，进行了红荧烯的捕获实验和自由基陷阱 DMPO 的电子顺磁共振 (EPR) 研究。这些实验的结果与自由基物种的中间性一致，并提出了一种新的、更温和的合成方法来生成
• Glycosidase inhibitors and methods of synthesizing same
  申请人：Pinto Mario Brian

  公开号：US20050065139A1

  公开（公告）日：2005-03-24

  A method for synthesizing Salacinol, its stereoisomers, and analogues, homologues and other derivatives thereof potentially useful as glycolsidase inhibitors. The compounds of the invention may have the general formula (I) or (II): The synthetic schemes comprise reacting a cyclic sulfate with a 5-membered ring sugar containing a heteroatom (X). The heteroatom preferably comprises sulfur, selenium, or nitrogen. The cyclic sulfate and ring sugar reagents may be readily prepared from carbohydrate precursors, such as D-glucose, L-glucose, D-xylose and L-xylose. The target compounds are prepared by opening of the cyclic sulfates by nucleophilic attack of the heteroatoms on the 5-membered ring sugars. The resulting heterocyclic compounds have a stable, inner salt structure comprising a heteroatom cation and a sulfate anion. The synthetic schemes yield various stereoisomers of the target compounds in moderate to good yields with limited side-reactions.

  一种合成Salacinol及其立体异构体、类似物、同系物和其他衍生物的方法，可能用作糖苷酶抑制剂。本发明的化合物可能具有一般式(I)或(II)：合成方案包括将环状硫酸酯与含有杂原子(X)的5元环糖反应。杂原子优选包括硫、硒或氮。环状硫酸酯和环糖试剂可以从碳水化合物前体（如D-葡萄糖、L-葡萄糖、D-木糖和L-木糖）中轻松制备。目标化合物是通过杂原子对5元环糖的亲核攻击打开环状硫酸酯来制备的。所得的杂环化合物具有稳定的内盐结构，包括一个杂原子阳离子和一个硫酸酯阴离子。合成方案以中等至良好的产率产生目标化合物的各种立体异构体，副反应有限。
• New synthesis of alditol thiaheterocycles via ring closure of vicinal bis-cyclic thionocarbonates of alditols
  作者：Sami Halila、Mohammed Benazza、Gilles Demailly

  DOI：10.1016/s0040-4039(01)02282-1

  日期：2002.1

  A new thiaheterocyclisation of alditols involving bis-cyclic thionocarbonate derivatives as bielectrophilic intermediates is reported. The polyhydroxylated tetrahydrothiophene, tetrahydropyrane and thiepane rings from erythritol, D,L-threitol, D-arabinitol, D-mannitol and galactitol were efficiently obtained. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Expedious synthesis of polyhydroxylated selena and thia-heterocycles via Se and S-ring closure of α,ω-dibromoalditols
  作者：Mohammed Benazza、Sami Halila、Camille Viot、Alain Danquigny、Christèle Pierru、Gilles Demailly

  DOI：10.1016/j.tet.2004.01.061

  日期：2004.3

  The selena and thiaanhydro alditols (with xylo, ribo, D-arabino, erythro, D,L-threo and D-manno configuration) were easily and expeditiously synthesized in good to excellent yields by reaction of selenure and sulfur ions as binucleophiles with alpha,omega-dibromoalditols as bis-electrophilic substrates. With the 1,6-dibromo-D-glucitol derivative as substrate, only the corresponding thiepane derivative was obtained while the selenaheterocyclistation attempte led to complex mixture. (C) 2004 Elsevier Ltd. All rights reserved.
• NaBH3CN and other systems as substitutes of tin and silicon hydrides in the light or heat-initiated reduction of halosugars: a tunable access to either 2-deoxy sugars or 1,5-anhydro-itols
  作者：Isabelle Bruyère、Zoltan Tóth、Hamida Benyahia、Jia Lu Xue、Jean-Pierre Praly

  DOI：10.1016/j.tet.2013.09.032

  日期：2013.11

  UV light-promoted reduction of acetobromoglucose by NaBH3CN in t-BuOH afforded 1,3,4,6-tetra-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranose in high yield and purity, via a Surzur-Tanner rearrangement, while, with 10 mol % thiophenol added, acetylated 1,5-anhydro-D-glucitol was cleanly obtained. Such tin-free and mild reductions, presumed to proceed via radical pathways, were more efficient with NaBH3CN compared to NaBH4 or NaBD4, and do not occur with acetochloroglucose. Similar reductions to 1,3,4,6-tetra-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranose were achieved upon heating to 80 degrees C t-BuOH or CH3CN solutions of NaBH3CN and AIBN, but with a lower selectivity due to competing ionic reactions. With other pyranosyl bromides, reductions by NaBH3CN could be tuned similarly (D-galacto), but some (D-manno, 5-thio-D-xylo) gave mainly or exclusively 1,5-anhydro-itols. Other conditions, or reagents promoting SET process, afforded also reduced products, but with lower rates or selectivities. Primary iodides were reduced readily with NaBH3CN under UV light. (c) 2013 Elsevier Ltd. All rights reserved.