(+)-3-oxo-1αH,7αH,10αH-guaia-4,11-dien-12-al | 952491-04-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-3-oxo-1αH,7αH,10αH-guaia-4,11-dien-12-al
• 英文别名: 2-[(5R,8S,8aS)-3,8-dimethyl-2-oxo-4,5,6,7,8,8a-hexahydro-1H-azulen-5-yl]prop-2-enal
• CAS: 952491-04-2
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: BLAATKSKYFFENW-BIMULSAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-3-oxo-1αH,7αH,10αH-guaia-4,11-dien-12-al 在 sodium chlorite 、 potassium dihydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 水 、 丙酮 为溶剂， 反应 3.0h， 以3.9 mg的产率得到一枝蒿酮酸
  参考文献：
  名称：

  戊二酸和油酸的不对称合成

  摘要：

  在该报告中，有效地合成了最初提出的鼠李酮酸（5）和油酸（3）。从皂苷苷的降解中回收的手性内酯13被用于制备关键的手性片段11。在探索这种聚合组装策略的过程中，闭环复分解（RCM），SmI 2提示分子间加成和[2,3] -Wittig重排被证明是合成亚基的有效方法。

  DOI：

  10.1021/acs.orglett.7b03459
• 作为产物：
  描述：

  1α,7α,10αH-guaia-4,11-dien-3-one 在 3,5-二甲基吡唑 、 chromium(VI) oxide 、 叔丁基过氧化氢 、 selenium(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 40.67h， 生成 (+)-3-oxo-1αH,7αH,10αH-guaia-4,11-dien-12-al
  参考文献：
  名称：

  Synthesis of (+)-pechueloic acid and (+)-aciphyllene. Revision of the structure of (+)-aciphyllene

  摘要：

  1 alpha H,7 alpha H,10 alpha H-Guaia-4,11-dien-3-one and its 1 beta H,10 beta H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1 alpha H,10 alpha H isomer gave as main product its 13- hydroxy derivative and a small amount of (+)-7 beta-hydroxy-1 alpha H,10 alpha H-guaia-4,11-dien-3-one, whereas the 1 beta H, 10 beta H diastereomer afforded selectively the (-)-7 alpha-hydroxy-1 beta H,10 beta H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C-3 of the 1 beta H,10 beta H guaiadienone afforded a guaiadiene with the reported structure for aciphyllene but its spectral data did not agree with those reported for the natural diene. The structure of natural (+)-aciphyllene has been corrected to 1 alpha H,7 alpha H,10 alpha H-guaia-4,11-diene obtained by deoxygenation of the 1 alpha H,10 alpha H guaiadienone. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.07.039

文献信息

• 一种制备一枝蒿酮酸的方法
  申请人：复旦大学

  公开号：CN109748787B

  公开（公告）日：2021-09-07

  本发明属药物合成技术领域，涉及一种制备一枝蒿酮酸的方法，该方法实现了一枝蒿酮酸(Rupestonic Acid/Pechueloic acid)的首次不对称合成。所述方法具有发散式合成特点，可通过分别改变中间体片段，得到多个一枝蒿酮酸的衍生物，为筛选具有更好生物活性的化合物提供了一种方法。通过对所述一枝蒿酮酸的全合成，并与天然分离的一枝蒿酮酸样品进行旋光、核磁数据及HPLC对照，将其结构由(5S,8S,8aS)矫正成(5R,8S,8aS)，证实所述一枝蒿酮酸(Rupestonic Acid)与具有Pechueloic acid相同的化学结构和立体构型。
• Synthesis of (+)-pechueloic acid and (+)-aciphyllene. Revision of the structure of (+)-aciphyllene
  作者：Gonzalo Blay、Begoña Garcia、Eva Molina、José R. Pedro

  DOI：10.1016/j.tet.2007.07.039

  日期：2007.9

  1 alpha H,7 alpha H,10 alpha H-Guaia-4,11-dien-3-one and its 1 beta H,10 beta H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1 alpha H,10 alpha H isomer gave as main product its 13- hydroxy derivative and a small amount of (+)-7 beta-hydroxy-1 alpha H,10 alpha H-guaia-4,11-dien-3-one, whereas the 1 beta H, 10 beta H diastereomer afforded selectively the (-)-7 alpha-hydroxy-1 beta H,10 beta H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C-3 of the 1 beta H,10 beta H guaiadienone afforded a guaiadiene with the reported structure for aciphyllene but its spectral data did not agree with those reported for the natural diene. The structure of natural (+)-aciphyllene has been corrected to 1 alpha H,7 alpha H,10 alpha H-guaia-4,11-diene obtained by deoxygenation of the 1 alpha H,10 alpha H guaiadienone. (c) 2007 Elsevier Ltd. All rights reserved.
• Asymmetric Synthesis of Rupestonic Acid and Pechueloic Acid
  作者：Pan Han、Zhu Zhou、Chang-Mei Si、Xian-Yi Sha、Zheng-Yi Gu、Bang-Guo Wei、Guo-Qiang Lin

  DOI：10.1021/acs.orglett.7b03459

  日期：2017.12.15

  In this report, the originally proposed rupestonic acid (5) and pechueloic acid (3) were efficiently synthesized. The chiral lactone 13, recycled from the degradation of saponin glycosides, was utilized to prepare the key chiral fragment 11. During the exploration of this convergent assembly strategy, the ring-closing metathesis (RCM), SmI2-prompted intermolecular addition, and [2,3]-Wittig rearrangement

  在该报告中，有效地合成了最初提出的鼠李酮酸（5）和油酸（3）。从皂苷苷的降解中回收的手性内酯13被用于制备关键的手性片段11。在探索这种聚合组装策略的过程中，闭环复分解（RCM），SmI 2提示分子间加成和[2,3] -Wittig重排被证明是合成亚基的有效方法。