(3S,4S,4aR,6S,7R,8S,9S,9aS)-6-(methoxymethoxymethyl)-3,4,8-trimethyl-9-phenylmethoxy-7-tri(propan-2-yl)silyloxy-3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepin-2-one | 157392-49-9

• 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: (3S,4S,4aR,6S,7R,8S,9S,9aS)-6-(methoxymethoxymethyl)-3,4,8-trimethyl-9-phenylmethoxy-7-tri(propan-2-yl)silyloxy-3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepin-2-one
• CAS: 157392-49-9
• 化学式: C₃₁H₅₂O₇Si
• 分子量: 564.835
• InChiKey: DGPNKGXNDRERTF-DDIOVHFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.35
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (3S,4S,4aR,6S,7R,8S,9S,9aS)-6-(methoxymethoxymethyl)-3,4,8-trimethyl-9-phenylmethoxy-7-tri(propan-2-yl)silyloxy-3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepin-2-one 在 4-二甲氨基吡啶 、 四氧化锇 、 二甲基硫 、 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 sodium hydride 、 (1S,2S)-1,2-diphenyl-N¹,N²-bis(mesitylmethyl)ethane-1,2-diamine 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 43.08h， 生成 [(2R,3S,4S,4'S,4aR,6S,7R,8R,9S,9aS)-7-hydroxy-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]-6-yl]methyl 4-methylbenzenesulfonate
  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：

  (S)-3-[(2R,3S,4S,5S,6R,7S)-4-Benzyloxy-3-(1-ethoxy-ethoxy)-7-methoxymethoxymethyl-5-methyl-6-triisopropylsilanyloxy-oxepan-2-yl]-butan-1-ol 在 重铬酸吡啶 、 pyridine-SO3 complex 、 4 A molecular sieve 、 溶剂黄146 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 (3S,4S,4aR,6S,7R,8S,9S,9aS)-6-(methoxymethoxymethyl)-3,4,8-trimethyl-9-phenylmethoxy-7-tri(propan-2-yl)silyloxy-3,4,4a,6,7,8,9,9a-octahydropyrano[3,2-b]oxepin-2-one
  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

文献信息

• Synthetic Studies toward Ciguatoxin. Stereocontrolled Construction of the KLM Ring Fragment
  作者：Makoto Sasaki、Masayuki Inoue、Kazuo Tachibana

  DOI：10.1021/jo00083a008

  日期：1994.2

  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).
• Stereocontrolled Synthesis of the JKLM Ring Fragment of Ciguatoxin
  作者：Makoto Sasaki、Masayuki Inoue、Kuniyuki Takamatsu、Kazuo Tachibana

  DOI：10.1021/jo990988j

  日期：1999.12.1

  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.