(4R,4aS,8R,8aR)-8-[(R)-1-(tert-Butyl-dimethyl-silanyloxymethyl)-2-methyl-propyl]-4-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-6-methyl-3,4,4a,7,8,8a-hexahydro-1H-naphthalen-2-one | 583866-24-4

• 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: (4R,4aS,8R,8aR)-8-[(R)-1-(tert-Butyl-dimethyl-silanyloxymethyl)-2-methyl-propyl]-4-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-6-methyl-3,4,4a,7,8,8a-hexahydro-1H-naphthalen-2-one
• 英文别名: (4R,4aS,8R,8aR)-8-[(2R)-1-[tert-butyl(dimethyl)silyl]oxy-3-methylbutan-2-yl]-4-[(2S)-1-[(4-methoxyphenyl)methoxy]propan-2-yl]-6-methyl-3,4,4a,7,8,8a-hexahydro-1H-naphthalen-2-one
• CAS: 583866-24-4
• 化学式: C₃₃H₅₄O₄Si
• 分子量: 542.875
• InChiKey: VFLJUMPEDZAARH-MZMJYPAFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.32
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,4aS,8R,8aR)-8-[(R)-1-(tert-Butyl-dimethyl-silanyloxymethyl)-2-methyl-propyl]-4-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-6-methyl-3,4,4a,7,8,8a-hexahydro-1H-naphthalen-2-one 在 咪唑 、 盐酸 、 草酰氯 、 水 、 碘 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 3.66h， 生成 (S)-2-[(1R,4aR,5R,8aS)-5-((R)-1-Iodomethyl-2-methyl-propyl)-7-methyl-3-oxo-1,2,3,4,4a,5,6,8a-octahydro-naphthalen-1-yl]-propionaldehyde
  参考文献：
  名称：

  Exploratory Studies Aimed at a Synthesis of Vinigrol. 3. Evaluation of a Lactone Bridge as a Conformational Lock

  摘要：

  DIAGRAMEvaluated in the present investigation are possible synthetic approaches to vinigrol based on the involvement of lactone rings as tools for the conformational rigidification of functionalized cis-octalins. Emphasis was placed on the structural arrangements resident in 3 and 5. The first of these systems proved to be highly strained and inaccessible. Especially notable was the finding that hydroxy ketenes 14 and 21 could be isolated and shown not to be amenable to cyclization when heated. The stereocontrolled assembly of 5 was successfully accomplished through exploitation of a related synthetic pathway. However, neither this attractive intermediate nor its close relative 33 could be processed in a manner that delivered the vinigrol framework. Nonetheless, several features of the routes deployed offer the prospect of wider application in other contexts.

  DOI：

  10.1021/jo0484575
• 作为产物：
  描述：

  (1S,2S,4S,8R)-2-[(1E,3S)-4-(p-methoxybenzyloxy)-3-methyl-1-butenyl]-8-[(1R)-1-[(tert-butyldimethylsiloxy)methyl]-2-methylpropyl]-1-methylbicyclo[2.2.2]oct-5-en-2-ol 在 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 以72%的产率得到(4R,4aS,8R,8aR)-8-[(R)-1-(tert-Butyl-dimethyl-silanyloxymethyl)-2-methyl-propyl]-4-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-6-methyl-3,4,4a,7,8,8a-hexahydro-1H-naphthalen-2-one
  参考文献：
  名称：

  vinigrol的聚合对映选择性合成，这是一种结构新颖的二萜类化合物，具有有效的血小板聚集抑制和抗高血压特性。1.阴离子共生在辛基亚结构的构建中的应用。

  摘要：

  在0摄氏度存在MgBr（2）.OEt（2）的情况下，构建基块15和36e的耦合以exo立体选择性（3.2：1）进行，比不使用碳氢化合物37e时更有利于获得甲醇37e。加性（exo / endo = 1：5.7）。设置顺式八氢萘55的所有相关立体中心的关键转换是37e的氧阴离子加速的[3,3]-σ重排。一个显着的特征是在结构上强制采用了船状过渡态，该态可用于以全顺式排列方式正确设置四个邻甲硫氨酸氢。由于最初通过埃文斯恶唑烷酮方案对映选择性地安装了异丙基取代基，因此55转化为碘砜62的方法可以通过X射线晶体学确认所有绝对立体化学赋值。没有观察到分子内阴离子环化62以产生三环骨架。这种反应性的缺乏归因于构象因素，该构象因素抑制了正确的S（N）2反应轨迹的实现。

  DOI：

  10.1021/jo0301301

文献信息

• Convergent Enantioselective Synthesis of Vinigrol, an Architecturally Novel Diterpenoid with Potent Platelet Aggregation Inhibitory and Antihypertensive Properties. 1. Application of Anionic Sigmatropy to Construction of the Octalin Substructure
  作者：Leo A. Paquette、Ronan Guevel、Shuichi Sakamoto、In Ho Kim、Jason Crawford

  DOI：10.1021/jo0301301

  日期：2003.8.1

  The coupling of building blocks 15 and 36e in the presence of MgBr(2).OEt(2) at 0 degrees C proceeds with an exo stereoselectivity (3.2:1) considerably more advantageous for the acquisition of carbinol 37e than in the absence of the additive (exo/endo = 1:5.7). The pivotal transformation that sets all of the relevant stereocenters of the cis-octalin 55 is the oxyanionic-accelerated [3,3]-sigmatropic

  在0摄氏度存在MgBr（2）.OEt（2）的情况下，构建基块15和36e的耦合以exo立体选择性（3.2：1）进行，比不使用碳氢化合物37e时更有利于获得甲醇37e。加性（exo / endo = 1：5.7）。设置顺式八氢萘55的所有相关立体中心的关键转换是37e的氧阴离子加速的[3,3]-σ重排。一个显着的特征是在结构上强制采用了船状过渡态，该态可用于以全顺式排列方式正确设置四个邻甲硫氨酸氢。由于最初通过埃文斯恶唑烷酮方案对映选择性地安装了异丙基取代基，因此55转化为碘砜62的方法可以通过X射线晶体学确认所有绝对立体化学赋值。没有观察到分子内阴离子环化62以产生三环骨架。这种反应性的缺乏归因于构象因素，该构象因素抑制了正确的S（N）2反应轨迹的实现。
• Exploratory Studies Aimed at a Synthesis of Vinigrol. 3. Evaluation of a Lactone Bridge as a Conformational Lock
  作者：Leo A. Paquette、Ivan Efremov

  DOI：10.1021/jo0484575

  日期：2005.1.1

  DIAGRAMEvaluated in the present investigation are possible synthetic approaches to vinigrol based on the involvement of lactone rings as tools for the conformational rigidification of functionalized cis-octalins. Emphasis was placed on the structural arrangements resident in 3 and 5. The first of these systems proved to be highly strained and inaccessible. Especially notable was the finding that hydroxy ketenes 14 and 21 could be isolated and shown not to be amenable to cyclization when heated. The stereocontrolled assembly of 5 was successfully accomplished through exploitation of a related synthetic pathway. However, neither this attractive intermediate nor its close relative 33 could be processed in a manner that delivered the vinigrol framework. Nonetheless, several features of the routes deployed offer the prospect of wider application in other contexts.