litseaverticillol B

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: litseaverticillol B
• 英文别名: (4S,5R)-5-[(1Z)-2,6-dimethylhepta-1,5-dienyl]-4-hydroxy-2-methylcyclopent-2-en-1-one
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: IRYFKBHIOJHFLA-ZOAGNIGNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-methoxytrifluoromethylphenylacetyl chloride 、 litseaverticillol B 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 12.0h， 生成 (S)-3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid 5-((Z)-2,6-dimethyl-hepta-1,5-dienyl)-3-methyl-4-oxo-cyclopent-2-enyl ester
  参考文献：
  名称：

  Natural anti-HIV agents. Part 3: Litseaverticillols A–H, novel sesquiterpenes from Litsea verticillata

  摘要：

  Bioassay directed-fractionation led to the identification of litseaverticillols A-H (1-8) from the leaves and twigs of Litsea verticillata Hance. These new sesquiterpenes possess a unique skeleton that was recently designated as 'litseane'. The structures of these compounds were determined by spectroscopic means including I D and 2D NMR data. Structural configurations were determined by ROESY experiments. Mosher ester reactions and optical rotation measurements established the sesquiterpenes 1-8 as racemates. Isolates 1-8 inhibited HIV-1 replication in HOG.R5 cells with IC50 values ranging from 2 to 15 mug/ml (8-58 muM) while affecting the growth of HOG.R5 at concentrations 2-3-fold higher. Based on this data, structure-activity relationships can be discerned, suggesting compounds of this class are good candidates for analog production. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)01491-6
• 作为产物：
  描述：

  柠康酸酐 在 sodium tetrahydroborate 、 二甲基硫 、 四甲基乙二胺 、 仲丁基锂 、 氧气 、 亚甲兰 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 35.02h， 生成 litseaverticillol B
  参考文献：
  名称：

  仿生香豆素B，E，I和J的仿生全合成和litavereillill E的结构重新分配。

  摘要：

  [反应：见正文]通过以下方法，首次实现了紫杉醇B（1），E（2），I（4）和J（5）的全合成，以及邻苯二酚E（2）的结构重新分配。转换过程的仿生序列，在此过程中，[4 + 2]引发的级联反应和烯键反应均涉及单线态氧（（1）O（2）），形成了关键步骤。邻苯二酚E（3）结构的重新分配，使其包含烯丙基氢过氧化物，为我们的生物遗传假说提供了有力的支持。

  DOI：

  10.1021/ol0493610

文献信息

• Biomimetic Total Synthesis of Litseaverticillols B, E, I, and J and Structural Reassignment of Litseaverticillol E
  作者：Georgios Vassilikogiannakis、Ioannis Margaros、Tamsyn Montagnon

  DOI：10.1021/ol0493610

  日期：2004.6.1

  [reaction: see text] The first total synthesis of litseaverticillols B (1), E (2), I (4), and J (5) as well as the structural reassignment of litseaverticillol E (2) have been achieved by means of a biomimetic sequence of transformations during which a [4 + 2]-initiated reaction cascade and an ene reaction, both involving singlet oxygen ((1)O(2)), formed key steps. The reassignment of the structure

  [反应：见正文]通过以下方法，首次实现了紫杉醇B（1），E（2），I（4）和J（5）的全合成，以及邻苯二酚E（2）的结构重新分配。转换过程的仿生序列，在此过程中，[4 + 2]引发的级联反应和烯键反应均涉及单线态氧（（1）O（2）），形成了关键步骤。邻苯二酚E（3）结构的重新分配，使其包含烯丙基氢过氧化物，为我们的生物遗传假说提供了有力的支持。
• Enantioselective Synthesis of the (1<i>S</i>,5<i>R</i>)-Enantiomer of Litseaverticillols A and B
  作者：Akira MORITA、Hiromasa KIYOTA、Shigefumi KUWAHARA

  DOI：10.1271/bbb.60253

  日期：2006.10.23

  An enantioselective synthesis of the (1S,5R)-enantiomer of litseaverticillols A and B was accomplished in line with our previously reported synthetic pathway for their (1R,5S)-enantiomer. The use of “EtSCeCl2” prepared from EtSLi and CeCl3, instead of previously employed EtSLi itself, for the formation of thiol ester intermediates prevented any undesirable epimerization occurring in the process.

  根据我们之前报告的(1R,5S)-对映体的合成途径，我们完成了litseaverticillols A和B的(1S,5R)-对映体的对映选择性合成。使用由 EtSLi 和 CeCl3 制备的 "EtSCeCl2"，而不是之前使用的 EtSLi 本身来形成硫醇酯中间体，防止了在此过程中出现任何不希望发生的外延。
• Illustrating the Power of Singlet Oxygen Chemistry in a Synthetic Context: Biomimetic Syntheses of Litseaverticillols A-G, I and J and the Structural Reassignment of Litseaverticillol E
  作者：Georgios Vassilikogiannakis、Ioannis Margaros、Tamsyn Montagnon、Manolis Stratakis

  DOI：10.1002/chem.200401311

  日期：2005.10.7

  Biomimetic syntheses of the litseaverticillols A-G, I and J are reported herein. The syntheses rely heavily on the application of two different modes of reaction for photochemically generated singlet oxygen, namely, the [4+2] cycloaddition of singlet oxygen (1O2) with furans and the ene reaction of 1O2 with double bonds. The highlight of these syntheses is a one-pot cascade sequence, involving five

  本文报道了枯草麻木AG，I和J的仿生合成。合成很大程度上依赖于光化学生成的单线态氧的两种不同反应模式的应用，即单线态氧（1O2）与呋喃的[4 + 2]环加成反应和1O2与双键的烯反应。这些合成的亮点是一锅级联序列，涉及由[4 + 2]反应引发的五种合成操作，以形成功能齐全的联苯并香茅醇核心。然后使用一系列的区域选择性烯反应适当地官能化侧链。邻苯二酚E的合成（包括最初提出的结构和实际结构）都可以对该天然产物进行结构上的重新分配。
• Natural anti-HIV agents. Part 3: Litseaverticillols A–H, novel sesquiterpenes from Litsea verticillata
  作者：Hong-Jie Zhang、Ghee Teng Tan、Vu Dinh Hoang、Nguyen Van Hung、Nguyen Manh Cuong、Djaja Doel Soejarto、John M Pezzuto、Harry H.S Fong

  DOI：10.1016/s0040-4020(02)01491-6

  日期：2003.1

  Bioassay directed-fractionation led to the identification of litseaverticillols A-H (1-8) from the leaves and twigs of Litsea verticillata Hance. These new sesquiterpenes possess a unique skeleton that was recently designated as 'litseane'. The structures of these compounds were determined by spectroscopic means including I D and 2D NMR data. Structural configurations were determined by ROESY experiments. Mosher ester reactions and optical rotation measurements established the sesquiterpenes 1-8 as racemates. Isolates 1-8 inhibited HIV-1 replication in HOG.R5 cells with IC50 values ranging from 2 to 15 mug/ml (8-58 muM) while affecting the growth of HOG.R5 at concentrations 2-3-fold higher. Based on this data, structure-activity relationships can be discerned, suggesting compounds of this class are good candidates for analog production. (C) 2002 Elsevier Science Ltd. All rights reserved.