Trifluoro-methanesulfonic acid (2S,3R,5S,6R)-5-benzyloxy-6-benzyloxymethyl-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl ester | 632354-41-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Trifluoro-methanesulfonic acid (2S,3R,5S,6R)-5-benzyloxy-6-benzyloxymethyl-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl ester
• 英文别名: [(2S,3R,5S,6R)-5-phenylmethoxy-6-(phenylmethoxymethyl)-3-triethylsilyloxyoxan-2-yl]methyl trifluoromethanesulfonate
• CAS: 632354-41-7
• 化学式: C₂₈H₃₉F₃O₇SSi
• 分子量: 604.76
• InChiKey: VEPXKTDNIXLBGW-YAOOYPAMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  40
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  88.7
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  Trifluoro-methanesulfonic acid (2S,3R,5S,6R)-5-benzyloxy-6-benzyloxymethyl-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl ester 在 正丁基锂 、 对甲苯磺酸 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 4.75h， 生成 (2S,4aS,6R,7S,8aR)-7-benzyloxy-6-benzyloxymethyl-2-(tert-butyldiphenylsilyloxymethyl)octahydropyrano[3,2-b]pyran-3-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
• 作为产物：
  描述：

  (4aS,6R,7S,8aR)-7-Benzyloxy-6-benzyloxymethyl-2,2-di-tert-butyl-hexahydro-1,3,5-trioxa-2-sila-naphthalene 在 2,6-二甲基吡啶 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 18.25h， 生成 Trifluoro-methanesulfonic acid (2S,3R,5S,6R)-5-benzyloxy-6-benzyloxymethyl-3-triethylsilanyloxy-tetrahydro-pyran-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

文献信息

• Divergent Synthesis of Trans-Fused Polycyclic Ethers by a Convergent Oxiranyl Anion Strategy
  作者：Takeo Sakai、Ai Sugimoto、Hiroki Tatematsu、Yuji Mori

  DOI：10.1021/jo302267f

  日期：2012.12.21

  oxiranyl anion generated from an epoxy sulfone, followed by ring expansion, allowed for the incorporation of medium-sized ring ethers into the key intermediate. Subsequent acetal formation and reductive etherification afforded various octacycles containing seven- and eight-membered ether rings.

  对应于耶司毒素CDEFGHIJ环系统的八环聚醚以及G和/或I环修饰的类似物，是使用[X + 2 + Y]型从一种常见的中间体开始，以发散的方式合成的收敛方法。三氟甲磺酸酯与环氧砜产生的环氧乙烷基阴离子反应，然后进行环扩环，从而允许将中等大小的环醚掺入关键中间体中。随后的乙缩醛形成和还原性醚化反应得到了各种八环，其中包含七元和八元醚环。
• A simple convergent synthesis of trans-fused six-membered polycyclic ethers
  作者：Yuji Mori、Shinjiro Mitsuoka、Hiroshi Furukawa

  DOI：10.1016/s0040-4039(00)00558-x

  日期：2000.5

  highly convergent method for the synthesis of trans-fused polytetrahydropyrans was developed, which involves: (i) coupling of cyclic triflate with an acetylene unit; (ii) oxidation of acetylene to 1,2-diketone; (iii) formation of a trans-fused cyclic dihemiacetal; (iv) O-methylation of the dihemiacetal; and (v) stereoselective reduction of the diacetal to trans-fused oxane rings.

  开发了一种高度收敛的合成反式聚四氢吡喃的方法，该方法包括：（i）环三氟甲磺酸酯与乙炔单元的偶联；（ii）将乙炔氧化为1,2-二酮；（iii）形成反式稠合的环二乙缩醛；（iv）二半缩醛的O-甲基化；（v）将二缩醛立体选择性还原为反式稠合的恶烷环。