(2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-(tert-butyldiphenylsilyloxymethyl)hexahydro-1,5-dioxabenzocycloheptan-7-one | 632354-44-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-(tert-butyldiphenylsilyloxymethyl)hexahydro-1,5-dioxabenzocycloheptan-7-one
• 英文别名: (2R,3S,4aR,6S,9aS)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-phenylmethoxy-2-(phenylmethoxymethyl)-3,4,4a,8,9,9a-hexahydro-2H-pyrano[3,2-b]oxepin-7-one
• CAS: 632354-44-0
• 化学式: C₄₁H₄₈O₆Si
• 分子量: 664.914
• InChiKey: ADLDUHDTJLNNQM-OQZGELFMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  48
• 可旋转键数：
  13
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-(tert-butyldiphenylsilyloxymethyl)hexahydro-1,5-dioxabenzocycloheptan-7-one 在 palladium dihydroxide 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 、 氢气 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 三乙基硼氢化锂 、 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 13.59h， 生成 trifluoromethanesulfonic acid (2R,3S,4aR,5aS,6aR,10aS,11aR,13aS)-3-(tert-butyldimethylsilyloxy)-8,8,10a,11a-tetramethyldodecahydro-1,5,7,9,11-pentaoxabenzo [4,5]cyclohepta[1,2-b]naphthalen-2-ylmethyl ester
  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：

  三甲基硅烷化重氮甲烷 、 (2S,4aS,6R,7S,8aR)-7-benzyloxy-6-benzyloxymethyl-2-(tert-butyldiphenylsilyloxymethyl)octahydropyrano[3,2-b]pyran-3-one 在 3 A molecular sieve 、 三氟化硼乙醚 、 4-甲基苯磺酸吡啶 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 3.67h， 以60%的产率得到(2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-(tert-butyldiphenylsilyloxymethyl)hexahydro-1,5-dioxabenzocycloheptan-7-one
  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.