(R)-4-(benzyloxy)-1-((2R,7S,8R)-7-bromo-8-ethyl-3,6,7,8-tetrahydro-2H-oxocin-2-yl)butan-1-ol | 1093122-03-2

• 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: (R)-4-(benzyloxy)-1-((2R,7S,8R)-7-bromo-8-ethyl-3,6,7,8-tetrahydro-2H-oxocin-2-yl)butan-1-ol
• CAS: 1093122-03-2
• 化学式: C₂₀H₂₉BrO₃
• 分子量: 397.352
• InChiKey: FMDCHLSZJFPOGD-MTQWCTHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  24.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (R)-4-(benzyloxy)-1-((2R,7S,8R)-7-bromo-8-ethyl-3,6,7,8-tetrahydro-2H-oxocin-2-yl)butan-1-ol 在 苯基氯化硒 、 对甲苯磺酸 作用下， 以 乙腈 为溶剂， 以76%的产率得到
  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：

  4-(benzyloxy)-1-((2R,7S,8R)-7-bromo-8-ethyl-3,6,7,8-tetrahydro-2H-oxocin-2-yl)butan-1-one 在 L-Selectride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以96%的产率得到(R)-4-(benzyloxy)-1-((2R,7S,8R)-7-bromo-8-ethyl-3,6,7,8-tetrahydro-2H-oxocin-2-yl)butan-1-ol
  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

文献信息

• Structure Determination of a Chloroenyne from <i>Laurencia majuscula</i> Using Computational Methods and Total Synthesis
  作者：Erin D. Shepherd、Bryony S. Dyson、William E. Hak、Quynh Nhu N. Nguyen、Miseon Lee、Mi Jung Kim、Te-ik Sohn、Deukjoon Kim、Jonathan W. Burton、Robert S. Paton

  DOI：10.1021/acs.joc.8b02975

  日期：2019.5.3

  advances in spectroscopic methods through the latter part of the 20th century, the unequivocal structure determination of natural products can remain challenging, and inevitably, incorrect structures appear in the literature. Computational methods that allow the accurate prediction of NMR chemical shifts have emerged as a powerful addition to the toolbox of methods available for the structure determination

  尽管在20世纪后期，光谱学方法取得了许多进步，但对天然产物的明确结构测定仍具有挑战性，并且不可避免地，文献中出现了不正确的结构。可以精确预测NMR化学位移的计算方法作为一种功能强大的工具箱出现了，该工具箱可用于确定有机小分子的结构。在这里，我们报告了使用计算方法和总合成的强大组合，以及相同方法对诺托炔的结构确认，从劳伦西亚山茱中提取了一种小，立体化学丰富的天然产物的结构。此外，我们合成了另外三种Ma。majuscula非对映异构体恩尼（Eyne），并证明了计算能够从天然产物的32种可能的非对映异构体中区分出四种合成非对映异构体。这项工作成功的关键是，通过识别对相对立体化学变化最敏感的化学位移，分析计算数据以在每个非对映异构体之间提供最大的区别。计算方法在立体化学丰富的柔性有机分子的结构确定中的成功使用将使所有参与结构确定的人都可以放心地使用这些方法。
• Asymmetric Total Synthesis and Structure Confirmation of (+)-(3E)-Isolaurefucin Methyl Ether
  作者：Deukjoon Kim、Te-ik Sohn、Byungsook Kim、Robert S. Paton

  DOI：10.3987/com-17-s(t)1

  日期：——

  An asymmetric total synthesis and structure confirmation of (+)-(3E)-isolaurefucin methyl ether (2a) was accomplished. Our synthesis features two complementary routes to construct the alpha,alpha'-trans-2,8-dioxabicyclo[5.2.1]decane skeleton of the natural product from alpha,alpha'-trans-gamma,delta-unsaturated oxocene alcohol 7, namely, an intramolecular epoxide opening route and a novel methoxyetherification route based on organoseleniummediated oxonium ion formation/fragmentation. A computational analysis was performed to model the observed different fragmentation behaviors of the respective oxonium ions 8 and 8' derived from alpha,alpha'-trans- and alpha,alpha'-cis-gamma,delta-unsaturated oxocene alcohols 7 and 7' during the organoselenium-mediated oxonium ion formation/fragmentation. Regarding the possibility of the natural product being an artifact, the reactivity of chlorofucin surrogate 16 and neoprelaurefucin surrogate 16' during methanolysis was compared, the results were in good agreement with calculations.