(2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-[(2S,3R)-3-(tert-butyldiphenylsilyloxymethyl)-3-methyl-2-(toluene-4-sulfonyl)oxiranylmethyl]-7-methyl-7-(trimethylsilyloxy)octahydro-1,5-dioxabenzocyclohepten | 632354-54-2

• 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-[(2S,3R)-3-(tert-butyldiphenylsilyloxymethyl)-3-methyl-2-(toluene-4-sulfonyl)oxiranylmethyl]-7-methyl-7-(trimethylsilyloxy)octahydro-1,5-dioxabenzocyclohepten
• 英文别名: [(2R,3S,4aR,6S,7R,9aS)-6-[[(2S,3R)-3-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-methyl-2-(4-methylphenyl)sulfonyloxiran-2-yl]methyl]-7-methyl-3-phenylmethoxy-2-(phenylmethoxymethyl)-2,3,4,4a,6,8,9,9a-octahydropyrano[3,2-b]oxepin-7-yl]oxy-trimethylsilane
• CAS: 632354-54-2
• 化学式: C₅₆H₇₂O₉SSi₂
• 分子量: 977.419
• InChiKey: GLUFJKXIVBLSBX-IWIWMCIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.34
• 重原子数：
  68
• 可旋转键数：
  19
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-[(2S,3R)-3-(tert-butyldiphenylsilyloxymethyl)-3-methyl-2-(toluene-4-sulfonyl)oxiranylmethyl]-7-methyl-7-(trimethylsilyloxy)octahydro-1,5-dioxabenzocyclohepten 在 palladium dihydroxide 2,6-二甲基吡啶 、 ruthenium(IV) oxide 、 sodium tetrahydroborate 、 sodium periodate 、 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 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 六甲基磷酰三胺 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 7.67h， 生成 1-[(2S,3R,5S,6R)-3-[tert-butyl(dimethyl)silyl]oxy-6-methyl-5-phenylmethoxy-6-(2-phenylmethoxyethyl)oxan-2-yl]-4-[(1S,3R,5S,6R,8S,11R,13S,18R)-5-[tert-butyl(dimethyl)silyl]oxy-11,13,16,16-tetramethyl-2,7,12,15,17-pentaoxatetracyclo[9.8.0.03,8.013,18]nonadecan-6-yl]butane-2,3-dione
  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：

  Trifluoro-methanesulfonic acid (2R,3S,4aR,6S,7R,9aS)-3-benzyloxy-2-benzyloxymethyl-7-hydroxy-7-methyl-octahydro-1,5-dioxa-benzocyclohepten-6-ylmethyl ester 在 2,6-二甲基吡啶 、 正丁基锂 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 1.25h， 生成 (2R,3S,4aR,6S,9aS)-3-benzyloxy-2-benzyloxymethyl-6-[(2S,3R)-3-(tert-butyldiphenylsilyloxymethyl)-3-methyl-2-(toluene-4-sulfonyl)oxiranylmethyl]-7-methyl-7-(trimethylsilyloxy)octahydro-1,5-dioxabenzocyclohepten
  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.