2-[(2R,3R,4S,5S,6S)-3-hydroxy-6-methoxy-5-methyl-4-phenylmethoxyoxan-2-yl]acetonitrile | 157219-90-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-[(2R,3R,4S,5S,6S)-3-hydroxy-6-methoxy-5-methyl-4-phenylmethoxyoxan-2-yl]acetonitrile
• CAS: 157219-90-4
• 化学式: C₁₆H₂₁NO₄
• 分子量: 291.347
• InChiKey: TXGOQWQZNZFTDB-AMMHQNNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  71.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-[(2R,3R,4S,5S,6S)-3-hydroxy-6-methoxy-5-methyl-4-phenylmethoxyoxan-2-yl]acetonitrile 在 4 A molecular sieve 2,6-二甲基吡啶 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium chlorite 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate 、 N-碘代丁二酰亚胺 、 重铬酸吡啶 、 2-甲基-2-丁烯 、 D-(-)-酒石酸二乙酯 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 potassium tert-butylate 、 四丁基氟化铵 、 二异丁基氢化铝 、 溶剂黄146 、 三乙胺 、 N,N-二异丙基乙胺 、 苯磺酰氯 、 lithium hexamethyldisilazane 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 异辛烷 、 正己烷 、 二氯甲烷 、 水 、 甲苯 、 乙腈 、 叔丁醇 为溶剂， 反应 14.0h， 生成
  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：

  (2R,4aR,6S,7S,8S,8aS)-6-methoxy-7-methyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine 在 4-二甲氨基吡啶 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 2-[(2R,3R,4S,5S,6S)-3-hydroxy-6-methoxy-5-methyl-4-phenylmethoxyoxan-2-yl]acetonitrile
  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

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.