(2R,3S,4aR,5aS,6aR,10aS,11aR,13aS)-3-benzyloxy-2-benzyloxymethyl-8,8,10a,11a-tetramethyldodecahydro-1,5,7,9,11-pentaoxabenzo[4,5]cyclohepta[1,2-b]naphthalene | 632354-57-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4aR,5aS,6aR,10aS,11aR,13aS)-3-benzyloxy-2-benzyloxymethyl-8,8,10a,11a-tetramethyldodecahydro-1,5,7,9,11-pentaoxabenzo[4,5]cyclohepta[1,2-b]naphthalene
• 英文别名: (1S,3R,5S,6R,8S,11R,13S,18R)-11,13,16,16-tetramethyl-5-phenylmethoxy-6-(phenylmethoxymethyl)-2,7,12,15,17-pentaoxatetracyclo[9.8.0.03,8.013,18]nonadecane
• CAS: 632354-57-5
• 化学式: C₃₃H₄₄O₇
• 分子量: 552.708
• InChiKey: LJGBETWZPJROIW-VPSHTCHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,3S,4aR,5aS,6aR,10aS,11aR,13aS)-3-benzyloxy-2-benzyloxymethyl-8,8,10a,11a-tetramethyldodecahydro-1,5,7,9,11-pentaoxabenzo[4,5]cyclohepta[1,2-b]naphthalene 在 palladium dihydroxide 2,6-二甲基吡啶 、 正丁基锂 、 氢气 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.75h， 生成 tert-butyl-[[(1S,3R,5S,6R,8S,11R,13S,18R)-6-[4-[(2S,3R,5S,6R)-3-[tert-butyl(dimethyl)silyl]oxy-6-methyl-5-phenylmethoxy-6-(2-phenylmethoxyethyl)oxan-2-yl]but-2-ynyl]-11,13,16,16-tetramethyl-2,7,12,15,17-pentaoxatetracyclo[9.8.0.03,8.013,18]nonadecan-5-yl]oxy]-dimethylsilane
  参考文献：
  名称：

  Sulfonyl-Stabilized Oxiranyllithium-Based Approach to Polycyclic Ethers. Convergent Synthesis of the ABCDEF-Ring System of Yessotoxin and Adriatoxin

  摘要：

  Convergent synthesis of the ABCDEF-ring system of yessotoxin and adriatoxin, marine polycyclic ether toxins causative of diarrheic shellfish poisoning, has been accomplished. The A-ring fragment was constructed by coupling of an appropriately functionalized sulfonyl-stabilized oxiranyl anion and a triflate prepared from an erythritol derivative. An iterative protocol of the oxiranyl anion strategy was also applied for the construction of the DEF-ring fragment. The triflate derivatives of the A-ring and the DEF-ring fragments were connected with lithium acetylide. The resulting acetylene derivative was further transformed into the hexacyclic ABCDEF fragment via oxidation of the acetylene unit to 1,2-diketone, double methyl acetal formation, and reductive etherification.

  DOI：

  10.1021/jo035145d
• 作为产物：
  描述：

  (2R,3S,4aR,6S,7S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-(tert-butyldiphenylsilyloxymethyl)hexahydro-1,5-dioxabenzocycloheptane-7-spiro-2'-oxirane 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 正丁基锂 、 三氟化硼乙醚 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 正己烷 、 二氯甲烷 为溶剂， 反应 7.84h， 生成 (2R,3S,4aR,5aS,6aR,10aS,11aR,13aS)-3-benzyloxy-2-benzyloxymethyl-8,8,10a,11a-tetramethyldodecahydro-1,5,7,9,11-pentaoxabenzo[4,5]cyclohepta[1,2-b]naphthalene
  参考文献：
  名称：

  Sulfonyl-Stabilized Oxiranyllithium-Based Approach to Polycyclic Ethers. Convergent Synthesis of the ABCDEF-Ring System of Yessotoxin and Adriatoxin

  摘要：

  Convergent synthesis of the ABCDEF-ring system of yessotoxin and adriatoxin, marine polycyclic ether toxins causative of diarrheic shellfish poisoning, has been accomplished. The A-ring fragment was constructed by coupling of an appropriately functionalized sulfonyl-stabilized oxiranyl anion and a triflate prepared from an erythritol derivative. An iterative protocol of the oxiranyl anion strategy was also applied for the construction of the DEF-ring fragment. The triflate derivatives of the A-ring and the DEF-ring fragments were connected with lithium acetylide. The resulting acetylene derivative was further transformed into the hexacyclic ABCDEF fragment via oxidation of the acetylene unit to 1,2-diketone, double methyl acetal formation, and reductive etherification.

  DOI：

  10.1021/jo035145d

文献信息

• Sulfonyl-Stabilized Oxiranyllithium-Based Approach to Polycyclic Ethers. Convergent Synthesis of the ABCDEF-Ring System of Yessotoxin and Adriatoxin
  作者：Yuji Mori、Kouichi Nogami、Hiasafumi Hayashi、Ryoji Noyori

  DOI：10.1021/jo035145d

  日期：2003.11.1

  Convergent synthesis of the ABCDEF-ring system of yessotoxin and adriatoxin, marine polycyclic ether toxins causative of diarrheic shellfish poisoning, has been accomplished. The A-ring fragment was constructed by coupling of an appropriately functionalized sulfonyl-stabilized oxiranyl anion and a triflate prepared from an erythritol derivative. An iterative protocol of the oxiranyl anion strategy was also applied for the construction of the DEF-ring fragment. The triflate derivatives of the A-ring and the DEF-ring fragments were connected with lithium acetylide. The resulting acetylene derivative was further transformed into the hexacyclic ABCDEF fragment via oxidation of the acetylene unit to 1,2-diketone, double methyl acetal formation, and reductive etherification.