(Z)-(2R,4aR,6S,7R,11aS)-6-[2-(Diphenyl-phosphinoyl)-ethyl]-7-(1-methoxy-1-methyl-ethoxy)-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononene | 221388-96-1

• 分子结构分类: 有机化合物
• 英文名称: (Z)-(2R,4aR,6S,7R,11aS)-6-[2-(Diphenyl-phosphinoyl)-ethyl]-7-(1-methoxy-1-methyl-ethoxy)-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononene
• CAS: 221388-96-1
• 化学式: C₃₄H₄₁O₆P
• 分子量: 576.67
• InChiKey: JBVUVKHGGDWLIL-HIQPJPRJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.38
• 重原子数：
  41.0
• 可旋转键数：
  9.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  63.22
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (Z)-(2R,4aR,6S,7R,11aS)-6-[2-(Diphenyl-phosphinoyl)-ethyl]-7-(1-methoxy-1-methyl-ethoxy)-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononene 在 正丁基锂 、 potassium hydride 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.83h， 生成 (Z)-(2R,4aR,6S,7R,11aS)-7-(1-Methoxy-1-methyl-ethoxy)-2-phenyl-6-((Z)-3-phenyl-allyl)-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononene
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 4: Final Stages and Completion

  摘要：

  The total synthesis of brevetoxin A is described, Our methodology of palladium-catalyzed couplings with cyclic ketene acetal phosphates was utilized to functionalize nine-membered ring lactone 4 followed by a [4+2] singlet oxygen addition to the resulting 1,3-diene (6), The product endoperoxide (7) was transformed into coupling partners 3a and 3b to be reacted with aldehyde 2, Our first attempted union of 3a and aldehyde 2 failed, most probably due to steric hindrance, which led us to explore other olefination coupling reactions. Horner- Wittig type coupling was found to be successful on advanced model systems: diphenylphosphine oxides 21 and 28 were each coupled with aldehyde 2. Key intermediates 3b and 2 were successfully coupled and ring F oxocene (44) was cyclized through the hydroxy dithioketal cyclization methodology, The final manipulations were then executed to complete the first total synthesis of brevetoxin A.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<646::aid-chem646>3.0.co;2-e
• 作为产物：
  描述：

  Methanesulfonic acid 2-[(Z)-(2R,4aR,6S,7R,11aS)-7-(1-methoxy-1-methyl-ethoxy)-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononen-6-yl]-ethyl ester 在 六甲基磷酰三胺 、 水 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 (Z)-(2R,4aR,6S,7R,11aS)-6-[2-(Diphenyl-phosphinoyl)-ethyl]-7-(1-methoxy-1-methyl-ethoxy)-2-phenyl-4a,6,7,8,11,11a-hexahydro-4H-1,3,5-trioxa-benzocyclononene
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 4: Final Stages and Completion

  摘要：

  The total synthesis of brevetoxin A is described, Our methodology of palladium-catalyzed couplings with cyclic ketene acetal phosphates was utilized to functionalize nine-membered ring lactone 4 followed by a [4+2] singlet oxygen addition to the resulting 1,3-diene (6), The product endoperoxide (7) was transformed into coupling partners 3a and 3b to be reacted with aldehyde 2, Our first attempted union of 3a and aldehyde 2 failed, most probably due to steric hindrance, which led us to explore other olefination coupling reactions. Horner- Wittig type coupling was found to be successful on advanced model systems: diphenylphosphine oxides 21 and 28 were each coupled with aldehyde 2. Key intermediates 3b and 2 were successfully coupled and ring F oxocene (44) was cyclized through the hydroxy dithioketal cyclization methodology, The final manipulations were then executed to complete the first total synthesis of brevetoxin A.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<646::aid-chem646>3.0.co;2-e