2,3,4,5-tetra-O-acetyl-1,6-anhydro-1-thio-D-mannitol | 351532-68-8

• 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: 2,3,4,5-tetra-O-acetyl-1,6-anhydro-1-thio-D-mannitol
• 英文别名: 2,3,4,5-tetra-O-acetyl-1,6-dideoxy-1,6-thio-D-mannitol；[(3S,4S,5S,6S)-4,5,6-triacetyloxythiepan-3-yl] acetate
• CAS: 351532-68-8
• 化学式: C₁₄H₂₀O₈S
• 分子量: 348.374
• InChiKey: IUTTUVFRKKSKKS-AAVRWANBSA-N

物化性质

• 熔点：
  93-95 °C
• 沸点：
  404.6±45.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  2,3,4,5-tetra-O-acetyl-1,6-anhydro-1-thio-D-mannitol 在 N-氯代丁二酰亚胺 、 zinc(II) oxide 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 31.0h， 生成 4-nitrophenyl 2,3,4,5-tetra-O-acetyl-1,6-dithio-α-D-mannoseptanoside
  参考文献：
  名称：

  具有抗血栓形成活性的4-氰基和4-硝基苯基的1,6-二硫代-D-甘露糖苷，L-氨基-和D-葡萄糖苷的合成。

  摘要：

  1,6-脱水-3,4-O-异亚丙基-1-硫代-D-甘露糖醇转化为亚砜，水解，乙酰化和随后的Pummerer重排后得到五-O-乙酰基-1-硫代-D-甘露糖庚糖异构体，收率优异。该异头混合物被用作供体，分别在三氟化硼醚化物和三甲基甲硅烷基三氟甲磺酸盐的存在下进行4-硝基-和4-氰基苯硫醇的糖基化反应，以高产率产生相应的硫代庚糖苷。使用1,6-脱水-3,4-O-异亚丙基-1-硫代-L-糖醇作为起始原料，将相同的策略应用于相应的L-亚氨基硫代糖苷的合成。五-O-乙酰基-D-葡糖硫庚糖供体不能以相同的方式合成，因为相应的四-O-乙酰基-1的Pummerer反应 6-硫代脱水-1-硫代-D-葡萄糖醇亚砜导致了相应的L-古洛糖基和D-葡糖硫代庚糖异构体的不可分离的混合物。因此，D-葡萄糖二乙基二硫缩醛通过其2,3,4,5-四-O-乙酰基-6-S-乙酰基衍生物被转化为其6-硫代-庚糖和-呋喃糖过乙酸酯的端

  DOI：

  10.1016/s0008-6215(02)00128-3
• 作为产物：
  描述：

  二溴甘露醇 在 吡啶 、 sodium sulfide 作用下， 以 二甲基亚砜 为溶剂， 反应 0.75h， 生成 2,3,4,5-tetra-O-acetyl-1,6-anhydro-1-thio-D-mannitol
  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

• 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.