(-)-gochnatiolides B | 87606-11-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (-)-gochnatiolides B
• 英文别名: (-)-gochnatiolide B；gochnatiolide A；gochnatiolide B；gochnatiolid B；(1R,2S,3'aS,6S,6'aR,9R,9'aR,9'bS,12R)-9-hydroxy-3',5,6',15-tetramethylidenespiro[3-oxatetracyclo[7.6.1.02,6.013,16]hexadec-13(16)-ene-12,9'-4,5,6a,7,9a,9b-hexahydro-3aH-azuleno[4,5-b]furan]-2',4,8',14-tetrone
• CAS: 87606-11-9
• 化学式: C₃₀H₃₀O₇
• 分子量: 502.564
• InChiKey: YBWJOCYIEKRETE-IGEADZBTSA-N

物化性质

• 熔点：
  195 °C (decomp)
• 沸点：
  801.4±65.0 °C(Predicted)
• 密度：
  1.38±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  37
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (-)-gochnatiolides B 在 盐酸 、 水 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 168.0h， 以27%的产率得到(-)-ainsliadimer B
  参考文献：
  名称：

  Biomimetic Syntheses of (−)-Gochnatiolides A–C and (−)-Ainsliadimer B

  摘要：

  We report the first biomimetic syntheses of (-)-gochnatiolides A-C and (-)-ainsliadimer B based on our proposed biogenetic pathway. Our synthesis features one-pot cascade transformations including Saegusa oxidation, intermolecular Diels-Alder cycloaddition, and radical-mediated allylic oxidation, which allow for the rapid generation of (-)-gochnatiolides A-C in a collective manner. We also disclose an unprecedented "copper effect" on the stereochemical outcome of the radical-mediated allylic oxidation. Our synthetic endeavors led to the structural reassignment of (-)-gochnatiolide B. Ultimately, a biomimetic transformation from gochnatiolide B to ainsliadimer B was achieved through a remarkable direct enone hydration.

  DOI：

  10.1021/ja305464s
• 作为产物：
  描述：

  (-)-ainsliadimer B 在 N,N'-二环己基碳二亚胺 、 copper(l) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以83%的产率得到(-)-gochnatiolides B
  参考文献：
  名称：

  Ainsliadimer B和Gonnatiolide A和B的总合成

  摘要：

  噢，我的天哪：用25个步骤完成了α-桑顿酸合成ainsliadimer B和gochnatiolide A和B的总产率约为1％。天然脱氢zaluzanin C与单体愈创木酚内酯衍生物的Diels-Alder反应可以立体选择性地组装二聚体gochnatiolide型骨架，并具有所需的立体化学和用于合成二聚体insinadimer B和gochnatiolides A和B的预装功能（参见方案）。

  DOI：

  10.1002/chem.201204292

文献信息

• Probing the Anticancer Mechanism of (−)-Ainsliatrimer A through Diverted Total Synthesis and Bioorthogonal Ligation
  作者：Chao Li、Ting Dong、Qiang Li、Xiaoguang Lei

  DOI：10.1002/anie.201407225

  日期：2014.11.3

  Herein, we report an efficient approach for exploring the novel anticancer mechanism of (−)‐ainsliatrimer A, a structurally complex and unique trimeric sesquiterpenoid, through a combined strategy of diverted total synthesis (DTS) and bioorthogonal ligation (TQ ligation), which allowed us to visualize the subcellular localization of this natural product in live cells. Further biochemical studies facilitated

  在本文中，我们报告了一种有效的方法，该方法通过改变总合成（DTS）和生物正交结扎（TQ结扎）的组合策略，探索一种结构复杂且独特的三聚倍半萜类化合物（-）-insaritritrimer A的新型抗癌机制。我们可视化这种天然产物在活细胞中的亚细胞定位。前靶标成像促进的进一步生化研究表明，核受体PPARγ是ainsliatrimer A的功能性细胞靶标。我们还证实了ainsliatrimer A的抗癌活性是由PPARγ的激活引起的。
• Biomimetic syntheses and structural elucidation of the apoptosis-inducing sesquiterpenoid trimers: (−)-ainsliatrimers A and B
  作者：Chao Li、Ting Dong、Longyang Dian、Weidong Zhang、Xiaoguang Lei

  DOI：10.1039/c2sc22023g

  日期：——

  Ainsliatrimers A and B are two recently isolated complex sesquiterpenoid natural products that display the unprecedented chemical motifs and remarkable anti-cancer activities. The exact structures as well as the mechanism of anti-cancer action for ainsliatrimers A and B remain to be elucidated. Here we report the first concise and biomimetic syntheses of (−)-ainsliatrimers A and B. Our synthetic endeavor ultimately enabled the unambiguous structural assignments for these two stunningly complex trimers. Preliminary biological studies also revealed that ainsliatrimers A and B significantly inhibited cancer cell growth by inducing apoptosis.

  Ainsliatrimers A 和 B 是最近分离的两种复杂的倍半萜类天然产物，它们表现出前所未有的化学基序和显着的抗癌活性。 ainsliatrimers A 和 B 的确切结构以及抗癌作用机制仍有待阐明。在这里，我们报告了 (α)-ainsliatrimers A 和 B 的首次简明仿生合成。我们的合成努力最终使这两个极其复杂的三聚体有了明确的结构分配。初步生物学研究还表明，ainsliatrimers A 和 B 通过诱导细胞凋亡显着抑制癌细胞生长。
• Total Syntheses of Ainsliadimer B and Gochnatiolides A and B
  作者：Dongliang Xia、Yu Du、Zhi Yi、Hao Song、Yong Qin

  DOI：10.1002/chem.201204292

  日期：2013.4.2

  syntheses of ainsliadimer B and gochnatiolides A and B from α‐santonin have been accomplished in 25 steps with approximately 1 % overall yield. A Diels–Alder reaction of natural dehydrozaluzanin C with a monomeric guaianolide derivative allows stereoselective assembly of a dimeric gochnatiolide‐type skeleton with the required stereochemistry and preinstalled functionalities for the synthesis of dimeric

  噢，我的天哪：用25个步骤完成了α-桑顿酸合成ainsliadimer B和gochnatiolide A和B的总产率约为1％。天然脱氢zaluzanin C与单体愈创木酚内酯衍生物的Diels-Alder反应可以立体选择性地组装二聚体gochnatiolide型骨架，并具有所需的立体化学和用于合成二聚体insinadimer B和gochnatiolides A和B的预装功能（参见方案）。
• Biomimetic Syntheses of (−)-Gochnatiolides A–C and (−)-Ainsliadimer B
  作者：Chao Li、Longyang Dian、Weidong Zhang、Xiaoguang Lei

  DOI：10.1021/ja305464s

  日期：2012.8.1

  We report the first biomimetic syntheses of (-)-gochnatiolides A-C and (-)-ainsliadimer B based on our proposed biogenetic pathway. Our synthesis features one-pot cascade transformations including Saegusa oxidation, intermolecular Diels-Alder cycloaddition, and radical-mediated allylic oxidation, which allow for the rapid generation of (-)-gochnatiolides A-C in a collective manner. We also disclose an unprecedented "copper effect" on the stereochemical outcome of the radical-mediated allylic oxidation. Our synthetic endeavors led to the structural reassignment of (-)-gochnatiolide B. Ultimately, a biomimetic transformation from gochnatiolide B to ainsliadimer B was achieved through a remarkable direct enone hydration.