((2R,3R,3aR,5S,6R,7S,8S,8aS)-2-Allyloxy-8-benzyloxy-5-methoxymethoxymethyl-3,7-dimethyl-octahydro-furo[3,2-b]oxepin-6-yloxy)-triisopropyl-silane | 259258-17-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((2R,3R,3aR,5S,6R,7S,8S,8aS)-2-Allyloxy-8-benzyloxy-5-methoxymethoxymethyl-3,7-dimethyl-octahydro-furo[3,2-b]oxepin-6-yloxy)-triisopropyl-silane
• CAS: 259258-17-8
• 化学式: C₃₂H₅₄O₇Si
• 分子量: 578.862
• InChiKey: JHSPFLMCDWRETM-DHEJKSMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.72
• 重原子数：
  40.0
• 可旋转键数：
  15.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  64.61
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  ((2R,3R,3aR,5S,6R,7S,8S,8aS)-2-Allyloxy-8-benzyloxy-5-methoxymethoxymethyl-3,7-dimethyl-octahydro-furo[3,2-b]oxepin-6-yloxy)-triisopropyl-silane 在 (1,5-cyclooctadiene)[bis(methyldiphenylphosphine)]iridium(I) hexafluorophosphate 、 氢气 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 1.16h， 生成 (2R,3S,4S,5S,6R,7S)-2-[(2S)-but-3-en-2-yl]-7-(methoxymethoxymethyl)-5-methyl-4-phenylmethoxy-6-tri(propan-2-yl)silyloxyoxepan-3-ol
  参考文献：
  名称：

  Stereocontrolled Synthesis of the JKLM Ring Fragment of Ciguatoxin

  摘要：

  A highly stereocontrolled synthesis of the JKLM ring fragment of ciguatoxin has been achieved. The present synthesis starts with methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-a-D whose configurations and substituents at C2-C5 correspond to those at C46-C49 of ciguatoxin, and involves as the key step base-induced 7-endo selective cyclization of a hydroxy epoxide for the efficient construction of the fully substituted oxepane ring K. Construction of the spiroether ring M was achieved by introduction of an allyl group to the ring L lactone followed by asymmetric dihydroxylation to install the C54 stereogenic center and acid-induced spiroketalization to furnish the protected KLM ring system. Finally, ring J was constructed by the method of Nicolaou to complete the synthesis of the JKLM ring fragment. The synthesis of a carboxylic acid derivative and its conjugation to carrier proteins to give an artificial antigen for development of an immunoassay system for the parent toxin molecule are also reported.

  DOI：

  10.1021/jo990988j
• 作为产物：
  描述：

  三异丙基硅基三氟甲磺酸酯 、 在 dimsylpotassium 、 2,6-二甲基吡啶 作用下， 以 四氢呋喃 、 二甲基亚砜 、 二氯甲烷 为溶剂， 以16.64 g的产率得到((2R,3R,3aR,5S,6R,7S,8S,8aS)-2-Allyloxy-8-benzyloxy-5-methoxymethoxymethyl-3,7-dimethyl-octahydro-furo[3,2-b]oxepin-6-yloxy)-triisopropyl-silane
  参考文献：
  名称：

  Stereocontrolled Synthesis of the JKLM Ring Fragment of Ciguatoxin

  摘要：

  A highly stereocontrolled synthesis of the JKLM ring fragment of ciguatoxin has been achieved. The present synthesis starts with methyl 4,6-O-benzylidene-2-deoxy-2-C-methyl-a-D whose configurations and substituents at C2-C5 correspond to those at C46-C49 of ciguatoxin, and involves as the key step base-induced 7-endo selective cyclization of a hydroxy epoxide for the efficient construction of the fully substituted oxepane ring K. Construction of the spiroether ring M was achieved by introduction of an allyl group to the ring L lactone followed by asymmetric dihydroxylation to install the C54 stereogenic center and acid-induced spiroketalization to furnish the protected KLM ring system. Finally, ring J was constructed by the method of Nicolaou to complete the synthesis of the JKLM ring fragment. The synthesis of a carboxylic acid derivative and its conjugation to carrier proteins to give an artificial antigen for development of an immunoassay system for the parent toxin molecule are also reported.

  DOI：

  10.1021/jo990988j