(1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-prop-2-enyl-2,8-dioxabicyclo[5.2.1]decan-6-ol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: (1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-prop-2-enyl-2,8-dioxabicyclo[5.2.1]decan-6-ol
• 化学式: C₁₃H₂₁BrO₃
• 分子量: 305.212
• InChiKey: NDJZOYJAVKAAFO-ZRFFIENRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  丁烯-2-醛 、 (1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-prop-2-enyl-2,8-dioxabicyclo[5.2.1]decan-6-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到(E)-4-[(1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-6-hydroxy-2,8-dioxabicyclo[5.2.1]decan-9-yl]but-2-enal
  参考文献：
  名称：

  Biomimetic Asymmetric Total Synthesis of (−)-Laurefucin via an Organoselenium-Mediated Intramolecular Hydroxyetherification

  摘要：

  The first asymmetric total synthesis of (-)-laurefucin (1), a unique C-15 acetogenin with a 2,8-dioxabicyclo[5.2.1]decane skeleton, has been accomplished in nine steps in 31% overall yield from known oxocene 10. Highlights of the highly stereoselective synthesis include a novel organoselenium-mediated biomimetic hydroxyetherification.

  DOI：

  10.1021/ja806304s
• 作为产物：
  描述：

  [(1S)-1-[(3aR,5R,7R,8S,9aR)-8-bromo-7-ethyl-2-oxo-4,5,7,8,9,9a-hexahydro-3aH-[1,3]dioxolo[4,5-d]oxocin-5-yl]but-3-enyl] methanesulfonate 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以46%的产率得到(1R,3R,4S,6R,7R,9R)-4-bromo-3-ethyl-9-prop-2-enyl-2,8-dioxabicyclo[5.2.1]decan-6-ol
  参考文献：
  名称：

  Concise Synthetic Approaches for the Laurencia Family: Formal Total Syntheses of (±)-Laurefucin and (±)-E- and (±)-Z-Pinnatifidenyne

  摘要：

  Herein is presented a cohesive strategy to rapidly fashion diverse members of the lauroxocane family of natural products, leading to the shortest syntheses of any member to date. These efforts include racemic formal total syntheses of laurefucin and E- and Z-pinnatifidenyne as well as a facile preparation of the oxocene core of 3E-dehydrobromolaurefucin. The key elements of the design are novel diastereoselective ring-expanding bromoetherifications of tetrahydrofurans triggered by a unique bromonium source (BDSB, Et2SBr center dot SbBrCl5) and strategically positioned nucleophilic traps, where altering the identity and position of these traps affords diverse functionality on the eight-membered ring backbone. Its biogenetic relevance is also discussed in light of the range of substrates that successfully undergo this key rearrangement.

  DOI：

  10.1021/ja3076988

文献信息

• Concise Synthetic Approaches for the Laurencia Family: Formal Total Syntheses of (±)-Laurefucin and (±)-<i>E</i>- and (±)-<i>Z</i>-Pinnatifidenyne
  作者：Scott A. Snyder、Alexandria P. Brucks、Daniel S. Treitler、Ioana Moga

  DOI：10.1021/ja3076988

  日期：2012.10.24

  Herein is presented a cohesive strategy to rapidly fashion diverse members of the lauroxocane family of natural products, leading to the shortest syntheses of any member to date. These efforts include racemic formal total syntheses of laurefucin and E- and Z-pinnatifidenyne as well as a facile preparation of the oxocene core of 3E-dehydrobromolaurefucin. The key elements of the design are novel diastereoselective ring-expanding bromoetherifications of tetrahydrofurans triggered by a unique bromonium source (BDSB, Et2SBr center dot SbBrCl5) and strategically positioned nucleophilic traps, where altering the identity and position of these traps affords diverse functionality on the eight-membered ring backbone. Its biogenetic relevance is also discussed in light of the range of substrates that successfully undergo this key rearrangement.
• Biomimetic Asymmetric Total Synthesis of (−)-Laurefucin via an Organoselenium-Mediated Intramolecular Hydroxyetherification
  作者：Byungsook Kim、Miseon Lee、Mi Jung Kim、Hyunjoo Lee、Sanghee Kim、Deukjoon Kim、Minseob Koh、Seung Bum Park、Kye Jung Shin

  DOI：10.1021/ja806304s

  日期：2008.12.10

  The first asymmetric total synthesis of (-)-laurefucin (1), a unique C-15 acetogenin with a 2,8-dioxabicyclo[5.2.1]decane skeleton, has been accomplished in nine steps in 31% overall yield from known oxocene 10. Highlights of the highly stereoselective synthesis include a novel organoselenium-mediated biomimetic hydroxyetherification.