4α-hydroperoxy-amorph-5-ene | 256643-65-9

• 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: 4α-hydroperoxy-amorph-5-ene
• 英文别名: 4α-hydroperoxy-5-amorphene；(1S,4R,4aS,7R)-7-hydroperoxy-4,7-dimethyl-1-propan-2-yl-2,3,4,4a,5,6-hexahydro-1H-naphthalene
• CAS: 256643-65-9
• 化学式: C₁₅H₂₆O₂
• 分子量: 238.37
• InChiKey: VFRUHIKTPCJDTE-UKTARXLSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4α-hydroperoxy-amorph-5-ene 在 氧气 、 三氟乙酸 作用下， 以 氘代氯仿 为溶剂， 生成 (1R,2S,3R,6S)-3-methyl-2-(3-oxobutyl)-6-propan-2-ylcyclohexane-1-carboxylic acid
  参考文献：
  名称：

  The role of the 12-carboxylic acid group in the spontaneous autoxidation of dihydroartemisinic acid

  摘要：

  Three of the four steps in the slow spontaneous autoxidation of dihydroartemisinic acid to artemisinin ('ene-type' reaction of molecular oxygen with the Delta(4.5) double bond, Hock cleavage of the resulting tertiary allylic hydroperoxide, oxygenation of the enol product from Hock cleavage and cyclization of the resulting vicinal hydroperoxyl-aldehyde to the 1,2,4-trioxane system of artemisinin) are shown to be assisted by the proximity of the 12-carboxylic acid functional group in dihydroartemisinic acid to the functional groups participating in these reactions. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01192-9
• 作为产物：
  描述：

  二氢青蒿酸 在 吡啶 、 盐酸 、 lithium aluminium tetrahydride 、 亚甲兰 作用下， 以 乙醚 、 氯仿 、 丙酮 为溶剂， 反应 43.5h， 生成 4α-hydroperoxy-amorph-5-ene
  参考文献：
  名称：

  青蒿素h的仿生合成和烯丙基氢过氧化物的3,2-重排

  摘要：

  酰基内过氧化物青蒿素H，是最近报道的来自青蒿的一种新型天然产物，是从二氢青蒿酸的光氧化过程中分两个步骤制得的，从而证实了有关其衍生自仲烯丙基氢过氧化物的生物遗传学推测。还讨论了这种烯丙基氢过氧化物很少研究的3，2-重排反应。

  DOI：

  10.1016/s0040-4020(99)00987-4

文献信息

• Biomimetic synthesis of arteannuin h and the 3,2-rearrangement of allylic hydroperoxides
  作者：Lai-King Sy、Koon-Sin Ngo、Geoffrey D. Brown

  DOI：10.1016/s0040-4020(99)00987-4

  日期：1999.12

  The acyl endoperoxide arteannuin H, recently reported as a novel natural product from Artemtsia annua, has been obtained in two steps from the photooxidation of dihydroartemisinic acid, thereby confirming biogenetic speculation regarding its derivation from a secondary allylic hydroperoxide. The little studied 3,2-rearrangement reaction of such allylic hydroperoxides is also discussed.

  酰基内过氧化物青蒿素H，是最近报道的来自青蒿的一种新型天然产物，是从二氢青蒿酸的光氧化过程中分两个步骤制得的，从而证实了有关其衍生自仲烯丙基氢过氧化物的生物遗传学推测。还讨论了这种烯丙基氢过氧化物很少研究的3，2-重排反应。
• Autoxidation of 4-amorphen-11-ol and the biogenesis of nor- and seco-amorphane sesquiterpenes from fabiana imbricata
  作者：Koon-Sin Ngo、Geoffrey D. Brown

  DOI：10.1016/s0040-4020(99)00986-2

  日期：1999.12

  Photooxidation of 4-amorphen-11-ol (1), recently reported as one of the major sesquiterpene natural products from the medicinal plant Fabiana imbricata, results in three allylic hydroperoxides 6, 9 and 10, which are expected from the “ene-type” reaction of molecular oxygen with the tri-substituted double bond in 1. The tertiary allylic hydroperoxide 6 undergoes carbon-carbon bond cleavage and a second

  的光氧化4- amorphen -11-醇（1），最近报道从药用植物的主要倍半萜烯天然产物之一法比亚纳玳瑁，结果在三个烯丙基氢过氧化物6，9和10，这是从“烯型预期在三取代的双键”分子氧的反应1。叔烯丙基氢过氧化物6所经受碳-碳键裂解和第二自氧化反应，得到更高度氧化开环-amorphane 11非常温和的条件下。然后在酸中，该化合物可能会经历第二个碳-碳键裂解反应，从而产生也不-sesquiterpenes 2和3（报告为真正从天然产物F.玳瑁，或环化倍半萜烯peroxofabianane（5），这是一种推测的前体的天然产物fabianane（4）。关于两个化学过程的一些机械的调查：即： -碳-碳键裂解和自氧化这将解释天然产物的形成2，3和4从1报告第三烯丙基氢过氧化物。32，它缺乏11-羟基官能团存在于1在更强的条件下仅经历C-4 / C-5碳-碳键裂解，表明该官能团在协助4-amorp
• The role of the 12-carboxylic acid group in the spontaneous autoxidation of dihydroartemisinic acid
  作者：Lai-King Sy、Geoffrey D Brown

  DOI：10.1016/s0040-4020(01)01192-9

  日期：2002.1

  Three of the four steps in the slow spontaneous autoxidation of dihydroartemisinic acid to artemisinin ('ene-type' reaction of molecular oxygen with the Delta(4.5) double bond, Hock cleavage of the resulting tertiary allylic hydroperoxide, oxygenation of the enol product from Hock cleavage and cyclization of the resulting vicinal hydroperoxyl-aldehyde to the 1,2,4-trioxane system of artemisinin) are shown to be assisted by the proximity of the 12-carboxylic acid functional group in dihydroartemisinic acid to the functional groups participating in these reactions. (C) 2002 Elsevier Science Ltd. All rights reserved.