(-)-tert-butyl-[(2R,4S,5S,6S,7S)-7-methoxymethoxymethyl-4,7-dimethyl-6-vinyl-1-oxaspiro[4.4]non-2-ylmethoxy]diphenylsilane | 890028-22-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (-)-tert-butyl-[(2R,4S,5S,6S,7S)-7-methoxymethoxymethyl-4,7-dimethyl-6-vinyl-1-oxaspiro[4.4]non-2-ylmethoxy]diphenylsilane
• 英文别名: tert-butyl-[[(2R,4S,5S,8S,9S)-9-ethenyl-8-(methoxymethoxymethyl)-4,8-dimethyl-1-oxaspiro[4.4]nonan-2-yl]methoxy]-diphenylsilane
• CAS: 890028-22-5
• 化学式: C₃₂H₄₆O₄Si
• 分子量: 522.8
• InChiKey: PHOIWAGCAMHYBJ-NEGUADISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.95
• 重原子数：
  37.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (-)-tert-butyl-[(2R,4S,5S,6S,7S)-7-methoxymethoxymethyl-4,7-dimethyl-6-vinyl-1-oxaspiro[4.4]non-2-ylmethoxy]diphenylsilane 在 9-borabicyclo[3.3.1]nonane dimer 、 sodium hydroxide 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 以100%的产率得到(-)-2-[(2R,4S,5S,6S,7S)-2-(tert-butyldiphenylsilanyloxymethyl)-7-methoxymethoxymethyl-1-oxaspiro[4.4]non-6-yl]ethanol
  参考文献：
  名称：

  Synthetic Studies on (+)-Ophiobolin A:  Asymmetric Synthesis of the Spirocyclic CD-Ring Moiety

  摘要：

  Asymmetric synthesis of the spirocyclic CID-ring moiety of (+)-ophiobolin A is described. Fragment A, which was prepared via pig liver esterase (PLE)-mediated kinetic resolution, and fragment B, which was prepared via diastereoselective allylation and subsequent kinetic iodolactonization, were coupled to afford the allylsilane 2, which was successfully cyclized to the desired spirocyclic CD-ring moiety la in the presence of a Lewis acid.

  DOI：

  10.1021/ol060437x
• 作为产物：
  描述：

  (3S,5R)-5-Iodomethyl-3-methyldihydrofuran-2(3H)-one 在 咪唑 、 Ti(OiPr)Cl3 、 叔丁基锂 、 sodium 2,2,2-trifluoroacetate 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 正戊烷 为溶剂， 反应 4.25h， 生成 (-)-tert-butyl-[(2R,4S,5S,6S,7S)-7-methoxymethoxymethyl-4,7-dimethyl-6-vinyl-1-oxaspiro[4.4]non-2-ylmethoxy]diphenylsilane
  参考文献：
  名称：

  Synthetic Studies on (+)-Ophiobolin A:  Asymmetric Synthesis of the Spirocyclic CD-Ring Moiety

  摘要：

  Asymmetric synthesis of the spirocyclic CID-ring moiety of (+)-ophiobolin A is described. Fragment A, which was prepared via pig liver esterase (PLE)-mediated kinetic resolution, and fragment B, which was prepared via diastereoselective allylation and subsequent kinetic iodolactonization, were coupled to afford the allylsilane 2, which was successfully cyclized to the desired spirocyclic CD-ring moiety la in the presence of a Lewis acid.

  DOI：

  10.1021/ol060437x

文献信息

• Enantioselective Total Synthesis of (+)-Ophiobolin A
  作者：Kazuhiro Tsuna、Naoyoshi Noguchi、Masahisa Nakada

  DOI：10.1002/chem.201204119

  日期：2013.4.22

  The enantioselective total synthesis of (+)‐ophiobolin A is described. This total synthesis features the construction of the spiro CD ring of (+)‐ophiobolin A through a stereoselective intramolecular Hosomi–Sakurai cyclization reaction, the joining of the A ring to the CD ring by using a reaction reported by Utimoto, and the construction of the ophiobolin eight‐membered carbocyclic ring through ring‐closing

  描述了（+）-ophiobolin A的对映选择性全合成。这种全合成的特征是通过立体选择性分子内Hosomi-Sakurai环化反应来构建（+）-ophiobolin A的螺旋CD环，利用Utimoto报道的反应将A环连接至CD环，以及构建ophiobolin通过闭环复分解（RCM）进行的八元碳环，这是本研究中首次进行。该成功的RCM反应需要使用在C5位含有苄氧基或甲氧基甲氧基且在C6位含有异丙烯基或其羟基化形式的底物。