Trifluoro-acetic acid (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-6-(2,2,2-trifluoro-acetoxy)-bicyclo[6.2.1]undec-2-en-1-yl ester | 200860-04-4

• 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: Trifluoro-acetic acid (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-6-(2,2,2-trifluoro-acetoxy)-bicyclo[6.2.1]undec-2-en-1-yl ester
• 英文别名: [(1S,2R,3S,4S,5S,6Z,8R)-2-(methoxymethoxy)-5-[(4S)-4-[(1R)-1-[(4-methoxyphenyl)methoxy]prop-2-enyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-4,11,11-trimethyl-8-(2,2,2-trifluoroacetyl)oxy-3-bicyclo[6.2.1]undec-6-enyl] 2,2,2-trifluoroacetate
• CAS: 200860-04-4
• 化学式: C₃₆H₄₆F₆O₁₀
• 分子量: 752.746
• InChiKey: FXWLWIPQXUBJFK-UVDWBIGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  52
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  Trifluoro-acetic acid (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-6-(2,2,2-trifluoro-acetoxy)-bicyclo[6.2.1]undec-2-en-1-yl ester 在 potassium carbonate 、 戴斯-马丁氧化剂 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (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：

  (1R,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-carbaldehyde 在 lithium aluminium tetrahydride 、 正丁基锂 、 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 乙醚 为溶剂， 反应 5.8h， 生成 Trifluoro-acetic acid (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-6-(2,2,2-trifluoro-acetoxy)-bicyclo[6.2.1]undec-2-en-1-yl ester
  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

文献信息

• 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
  作者：Jeffrey N. Johnston、Hon-Chung Tsui、Leo A. Paquette

  DOI：10.1021/jo971591n

  日期：1998.1.1

  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.