(1S,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-1-[(Z)-2-(phenylthio)vinyl]bicyclo[2.2.1]heptan-2-one | 200859-96-7

• 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: (1S,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-1-[(Z)-2-(phenylthio)vinyl]bicyclo[2.2.1]heptan-2-one
• 英文别名: (1S,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-1-[(Z)-2-phenylsulfanylethenyl]bicyclo[2.2.1]heptan-2-one
• CAS: 200859-96-7
• 化学式: C₁₉H₂₄O₃S
• 分子量: 332.464
• InChiKey: FXSJYUXBORNYPO-BAJSSTROSA-N

物化性质

• 熔点：
  70-70.5 °C
• 沸点：
  433.353±45.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.171±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：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-1-[(Z)-2-(phenylthio)vinyl]bicyclo[2.2.1]heptan-2-one 在 正丁基锂 、 18-冠醚-6 、 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 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.47h， 生成 (5E,7E)-(1S,2R,4S)-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]undeca-5,7-dien-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：

  (苯硫甲基)三苯基氯化鏻 、 (1R,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-carbaldehyde 在 双(三甲基硅烷基)氨基钾 作用下， 生成 (1S,3R,4S)-3-(methoxymethoxy)-7,7-dimethyl-1-[(Z)-2-(phenylthio)vinyl]bicyclo[2.2.1]heptan-2-one 、 (1S,3R,4S)-3-Methoxymethoxy-7,7-dimethyl-1-((E)-2-phenylsulfanyl-vinyl)-bicyclo[2.2.1]heptan-2-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

文献信息

• Heteroatomic Modulation of Oxyanionic Cope Rearrangement Rates. Consequences on Competing Nucleophilic Cleavage of an Oxetane Ring in Precursors to Paclitaxel
  作者：Leo A. Paquette、Hui-Ling Wang、Qingbei Zeng、Tzenge-Lien Shih

  DOI：10.1021/jo981059f

  日期：1998.9.1
• 10.1002/1099-0690(200006)2000:12<2187::aid-ejoc2187<3.0.co;2-2
  作者：Paquette, Leo、Zeng, Qingbei、Wang, Hui-Ling、Shih, Tzenge-Lien

  DOI：10.1002/1099-0690(200006)2000:12<2187::aid-ejoc2187<3.0.co;2-2

  日期：——
• 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.