(Z)-(1R,4S,5S,6S,7R,8S)-4-{(S)-4-[(R)-1-(4-Methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-7-methoxymethoxy-5,11,11-trimethyl-bicyclo[6.2.1]undec-2-ene-1,6-diol | 200860-05-5

• 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: (Z)-(1R,4S,5S,6S,7R,8S)-4-{(S)-4-[(R)-1-(4-Methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-7-methoxymethoxy-5,11,11-trimethyl-bicyclo[6.2.1]undec-2-ene-1,6-diol
• 英文别名: (1R,2Z,4S,5S,6S,7R,8S)-7-(methoxymethoxy)-4-[(4S)-4-[(1R)-1-[(4-methoxyphenyl)methoxy]prop-2-enyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-5,11,11-trimethylbicyclo[6.2.1]undec-2-ene-1,6-diol
• CAS: 200860-05-5
• 化学式: C₃₂H₄₈O₈
• 分子量: 560.728
• InChiKey: UMDRMSLKKRAADP-SAWZFGHISA-N

物化性质

• 沸点：
  632.281±55.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.166±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  95.8
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (Z)-(1R,4S,5S,6S,7R,8S)-4-{(S)-4-[(R)-1-(4-Methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-7-methoxymethoxy-5,11,11-trimethyl-bicyclo[6.2.1]undec-2-ene-1,6-diol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以93%的产率得到(Z)-(1S,2R,4S,5S,8R)-8-Hydroxy-5-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-2-methoxymethoxy-4,11,11-trimethyl-bicyclo[6.2.1]undec-6-en-3-one
  参考文献：
  名称：

  Application of an S → O Allylic Transposition in the Context of a Bridgehead Olefinic System. New Opportunities for the Structural Modification of Bicyclo[6.2.1]undecanes via Transannular Ring Closure

  摘要：

  A practical route is described for the preparation of allylic sulfide 8, whose double bond resides at a bridgehead site, Following hydride reduction of the ketone carbonyl and sulfoxidation, exposure to trifluoroacetic anhydride results in the operation of an intermolecular S --> O allylic transposition, This central step leads to 14a, an intermediate useful for probing the consequences associated with epoxidation of its cis-cyclononene double bond. A total of three different transannular cyclizations are described in order to demonstrate the ease with which ring closures can operate in a medium-ring setting of this type. Represented are transformations that generate tetrahydrofuran, oxetane, and cyclopropane subunits. The kinetic biases favoring these transformations are highlighted.

  DOI：

  10.1021/jo971591n
• 作为产物：
  描述：

  (1S,2S,3R,4S)-3-(methoxymethoxy)-2-[(Z)-2-[(4S)-4-[(1R)-1-[(4-methoxyphenyl)methoxy]prop-2-enyl]-2,2-dimethyl-1,3-dioxolan-4-yl]ethenyl]-7,7-dimethyl-1-[(Z)-2-phenylsulfanylethenyl]bicyclo[2.2.1]heptan-2-ol 在 lithium aluminium tetrahydride 、 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 3.75h， 生成 (Z)-(1R,4S,5S,6S,7R,8S)-4-{(S)-4-[(R)-1-(4-Methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-7-methoxymethoxy-5,11,11-trimethyl-bicyclo[6.2.1]undec-2-ene-1,6-diol
  参考文献：
  名称：

  Application of an S → O Allylic Transposition in the Context of a Bridgehead Olefinic System. New Opportunities for the Structural Modification of Bicyclo[6.2.1]undecanes via Transannular Ring Closure

  摘要：

  A practical route is described for the preparation of allylic sulfide 8, whose double bond resides at a bridgehead site, Following hydride reduction of the ketone carbonyl and sulfoxidation, exposure to trifluoroacetic anhydride results in the operation of an intermolecular S --> O allylic transposition, This central step leads to 14a, an intermediate useful for probing the consequences associated with epoxidation of its cis-cyclononene double bond. A total of three different transannular cyclizations are described in order to demonstrate the ease with which ring closures can operate in a medium-ring setting of this type. Represented are transformations that generate tetrahydrofuran, oxetane, and cyclopropane subunits. The kinetic biases favoring these transformations are highlighted.

  DOI：

  10.1021/jo971591n