(1S,2S,4S,5S,6R,8R,9S)-1,6-Dihydroxy-5-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-8-methoxymethoxy-6,12,12-trimethyl-3-oxa-tricyclo[7.2.1.0^2,4]dodecan-7-one | 200860-09-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,2S,4S,5S,6R,8R,9S)-1,6-Dihydroxy-5-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-8-methoxymethoxy-6,12,12-trimethyl-3-oxa-tricyclo[7.2.1.0^2,4]dodecan-7-one
• 英文别名: (1S,2S,4S,5S,6R,8R,9S)-1,6-dihydroxy-8-(methoxymethoxy)-5-[(4S)-4-[(1R)-1-[(4-methoxyphenyl)methoxy]prop-2-enyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-6,12,12-trimethyl-3-oxatricyclo[7.2.1.02,4]dodecan-7-one
• CAS: 200860-09-9
• 化学式: C₃₂H₄₆O₁₀
• 分子量: 590.711
• InChiKey: YVSKCFGHPFWNNW-ZZLZMFEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  42
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  125
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (1S,2S,4S,5S,6R,8R,9S)-1,6-Dihydroxy-5-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-8-methoxymethoxy-6,12,12-trimethyl-3-oxa-tricyclo[7.2.1.0^2,4]dodecan-7-one 在 氢氧化钾 作用下， 以 水 、 二甲基亚砜 为溶剂， 反应 2.0h， 以56%的产率得到1-((1S,2R,3S,5R,6S,7S,11R)-6,7-Dihydroxy-11-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-2-methoxymethoxy-10,10-dimethyl-4-oxa-tricyclo[5.2.1.1^3,5]undec-3-yl)-ethanone
  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：

  (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 在 18-冠醚-6 、 四丁基氟化铵 、 氧气 、 双(三甲基硅烷基)氨基钾 、 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 40.33h， 生成 (1S,2S,4S,5S,6R,8R,9S)-1,6-Dihydroxy-5-{(S)-4-[(R)-1-(4-methoxy-benzyloxy)-allyl]-2,2-dimethyl-[1,3]dioxolan-4-yl}-8-methoxymethoxy-6,12,12-trimethyl-3-oxa-tricyclo[7.2.1.0^2,4]dodecan-7-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