(2R,3S,4S,4'S,4aR,6S,7R,8R,9S,9aS)-7-methoxy-6-(methoxymethoxymethyl)-3,4,8-trimethyl-4',9-bis(phenylmethoxy)spiro[3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepine-2,2'-oxolane] | 157220-26-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S,4S,4'S,4aR,6S,7R,8R,9S,9aS)-7-methoxy-6-(methoxymethoxymethyl)-3,4,8-trimethyl-4',9-bis(phenylmethoxy)spiro[3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepine-2,2'-oxolane]
• CAS: 157220-26-3
• 化学式: C₃₃H₄₆O₈
• 分子量: 570.723
• InChiKey: YQOHZLGULGETEV-HOAHBMKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S,4'S,4aR,6S,7R,8R,9S,9aS)-7-methoxy-6-(methoxymethoxymethyl)-3,4,8-trimethyl-4',9-bis(phenylmethoxy)spiro[3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepine-2,2'-oxolane] 在 palladium dihydroxide 氢气 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以67%的产率得到(2R,3S,3'S,4S,4aR,6S,7R,8S,9S,9aS)-7-methoxy-6-(methoxymethoxymethyl)-3,4,8-trimethylspiro[3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepine-2,5'-oxolane]-3',9-diol
  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：

  [(2S,3R,4S,5S,6S,7R)-7-[(2S)-but-3-en-2-yl]-2-(methoxymethoxymethyl)-4-methyl-5-phenylmethoxy-6-triethylsilyloxyoxepan-3-yl]oxy-tri(propan-2-yl)silane 在 sodium hydroxide 、 四氧化锇 、 重铬酸吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 pyridine-SO3 complex 、 1,2-diphenyl-N,N'-bis[(2,4,6-trimethylphenyl)methyl]-1,2-diaminoethane 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 双氧水 、 potassium hydride 、 sodium hydride 、 sodium hydrogensulfite 、 溶剂黄146 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 (2R,3S,4S,4'S,4aR,6S,7R,8R,9S,9aS)-7-methoxy-6-(methoxymethoxymethyl)-3,4,8-trimethyl-4',9-bis(phenylmethoxy)spiro[3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepine-2,2'-oxolane]
  参考文献：
  名称：

  Synthetic Studies toward Ciguatoxin. Stereocontrolled Construction of the KLM Ring Fragment

  摘要：

  The first stereoselective synthesis of the KLM ring fragment of ciguatoxin is reported including as a key step 7-endo selective cyclization of epoxy alcohol to construct a fully substituted oxepane ring (12 --> 13).

  DOI：

  10.1021/jo00083a008