(3S,3aR,5S,6S,7S,7aS)-7-Benzyloxy-5-methoxy-3,6-dimethyl-hexahydro-furo[3,2-b]pyran-2-one | 259258-16-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃吡喃类
• 英文名称: (3S,3aR,5S,6S,7S,7aS)-7-Benzyloxy-5-methoxy-3,6-dimethyl-hexahydro-furo[3,2-b]pyran-2-one
• CAS: 259258-16-7
• 化学式: C₁₇H₂₂O₅
• 分子量: 306.359
• InChiKey: OFZWSDCXRUBUFD-BTVLNHBSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (3S,3aR,5S,6S,7S,7aS)-7-Benzyloxy-5-methoxy-3,6-dimethyl-hexahydro-furo[3,2-b]pyran-2-one 在 4 A molecular sieve 2,6-二甲基吡啶 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium tetrahydroborate 、 N-碘代丁二酰亚胺 、 重铬酸吡啶 、 D-(-)-酒石酸二乙酯 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 potassium tert-butylate 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 异辛烷 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 9.67h， 生成 (3R,4R,5S)-4-[tert-butyl(dimethyl)silyl]oxy-5-[(1S,2S)-2-[(2R,3R)-3-(methoxymethoxymethyl)oxiran-2-yl]-1-phenylmethoxypropyl]-3-methyloxolan-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
• 作为产物：
  描述：

  2-[(2R,3R,4S,5S,6S)-3-hydroxy-6-methoxy-5-methyl-4-phenylmethoxyoxan-2-yl]acetic acid 在 三乙胺 、 苯磺酰氯 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (3S,3aR,5S,6S,7S,7aS)-7-Benzyloxy-5-methoxy-3,6-dimethyl-hexahydro-furo[3,2-b]pyran-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