meso-3,6-Diacetoxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane | 159292-54-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: meso-3,6-Diacetoxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane
• 英文别名: meso-3,6-Diacetoxy-2,7-bis[(tert-butyldimethylsiloxy)methyl]-4,5-didehydrooxepane；[(2R,3S,6R,7S)-6-acetyloxy-2,7-bis[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3,6,7-tetrahydrooxepin-3-yl] acetate
• CAS: 159292-54-3
• 化学式: C₂₄H₄₆O₇Si₂
• 分子量: 502.796
• InChiKey: ZAUIPDMZODPYRP-ZDNVTZCJSA-N

物化性质

• 沸点：
  471.4±45.0 °C(predicted)
• 密度：
  1.01±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.22
• 重原子数：
  33
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  meso-3,6-Diacetoxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane 在 sodium hydroxide 、 phosphate buffer 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 (2R,3S,6R,7S)-3-Acetoxy-6-hydroxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034
• 作为产物：
  描述：

  (Z,Z)-2,6-Cyclooctadien-1-ol 在 Lindlar's catalyst 、 bis(acetylacetonate)oxovanadium 、 tetraphenylporphyrin 咪唑 、 喹啉 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium tetrahydroborate 、 sodium periodate 、 草酰氯 、 pyridine-SO3 complex 、 dimethyl sulfide borane 、 四丁基氟化铵 、 氢气 、 双氧水 、 碘 、 氧气 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 异辛烷 、 二氯甲烷 、 氯仿 、 水 、 二甲基亚砜 、 苯 为溶剂， 反应 122.83h， 生成 meso-3,6-Diacetoxy-2,7-bis<(tert-butyldimethylsiloxy)methyl>-4,5-didehydrooxepane
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034