(+/-)-α-agarofuran

• 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: (+/-)-α-agarofuran
• 英文别名: alpha-Agarofurane；(1S,6R,9S)-2,6,10,10-tetramethyl-11-oxatricyclo[7.2.1.01,6]dodec-2-ene
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: ZLQADKTVJQXDIG-NWANDNLSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-α-agarofuran 以 甲醇 为溶剂， 生成 (3aS,6R,8aS)-6-(1-Hydroxy-1-methyl-ethyl)-3a,8a-dimethyl-octahydro-azulen-4-one
  参考文献：
  名称：

  光引发的Wagner-Meerwein重排。初步沟通

  摘要：

  除了简单的双键迁移到β-agarofuran之外，在甲醇中辐照八氢化萘衍生的倍半萜烯氧化物α-agarofuran还会导致重排到过氢azulene系统。这种重排显然是通过类似碳离子的中间体进行的，而常规的碳正离子生成仅导致氧化物环打开而不进行重排。

  DOI：

  10.1002/hlca.19760590427
• 作为产物：
  描述：

  在 Wilkinson's catalyst 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以14.2 mg的产率得到(+/-)-α-agarofuran
  参考文献：
  名称：

  Rh(I)-Catalyzed [(3 + 2) + 1] Cycloaddition of 1-Yne/Ene-vinylcyclopropanes and CO: Homologous Pauson−Khand Reaction and Total Synthesis of (±)-α-Agarofuran

  摘要：

  A novel Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition, which can be regarded as a homologous Pauson-Khand reaction, was developed to synthesize bicyclic cyclohexenones and cyclohexanones, enabling a new approach for synthesis of six-membered carbocycles ubiquitously found in natural products and pharmaceutics. The significance of the Rh-catalyzed [(3 + 2) + 1] cycloaddition has been demonstrated by the total synthesis of a furanoid sesquiterpene natural product, a-agarofuran, in which the bicyclic skeleton was constructed by the [(3 + 2) + 1] reaction of 1-yne-VCP and CO.

  DOI：

  10.1021/ol100625e

文献信息

• Rh(I)-Catalyzed [(3 + 2) + 1] Cycloaddition of 1-Yne/Ene-vinylcyclopropanes and CO: Homologous Pauson−Khand Reaction and Total Synthesis of (±)-α-Agarofuran
  作者：Lei Jiao、Mu Lin、Lian-Gang Zhuo、Zhi-Xiang Yu

  DOI：10.1021/ol100625e

  日期：2010.6.4

  A novel Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition, which can be regarded as a homologous Pauson-Khand reaction, was developed to synthesize bicyclic cyclohexenones and cyclohexanones, enabling a new approach for synthesis of six-membered carbocycles ubiquitously found in natural products and pharmaceutics. The significance of the Rh-catalyzed [(3 + 2) + 1] cycloaddition has been demonstrated by the total synthesis of a furanoid sesquiterpene natural product, a-agarofuran, in which the bicyclic skeleton was constructed by the [(3 + 2) + 1] reaction of 1-yne-VCP and CO.
• A Photo-initiatedWagner-Meerwein Rearrangement. Preliminary communication
  作者：Alan F. Thomas、Michel Ozainne

  DOI：10.1002/hlca.19760590427

  日期：1976.6.2

  sesquiterpene oxide α-agarofuran in methanol leads to rearrangement to the perhydroazulene system, in addition to simple double-bond migration to β-agarofuran. This rearrangement apparently proceeds through a carbonium-ion-like intermediate, whereas conventional generation of a carbocation leads only to opening of the oxide ring without rearrangement.

  除了简单的双键迁移到β-agarofuran之外，在甲醇中辐照八氢化萘衍生的倍半萜烯氧化物α-agarofuran还会导致重排到过氢azulene系统。这种重排显然是通过类似碳离子的中间体进行的，而常规的碳正离子生成仅导致氧化物环打开而不进行重排。