(+)-alloaromadendrane-4α,10β-diol | 141610-47-1

• 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: (+)-alloaromadendrane-4α,10β-diol
• 英文别名: (1aR,4S,4aS,7S,7aS,7bR)-1,1,4,7-tetramethyl-1a,2,3,4a,5,6,7a,7b-octahydrocyclopropa[h]azulene-4,7-diol
• CAS: 141610-47-1
• 化学式: C₁₅H₂₆O₂
• 分子量: 238.37
• InChiKey: DWNPMJOWAWGIMM-GFCMYALRSA-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：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (1aR,4aS,7S,7aS,7bR)-1,1,7-Trimethyl-7-trimethylsilanyloxy-decahydro-cyclopropa[e]azulen-4-one 在 Oxone 、 lithium aluminium tetrahydride 、 18-冠醚-6 、 硫酸 、 碘 、 碳酸氢钠 、 magnesium 、 丙酮 作用下， 生成 (+)-alloaromadendrane-4α,10β-diol
  参考文献：
  名称：

  The synthesis of mono- and dihydroxy aromadendrane sesquiterpenes, starting from natural (+)-aromadendrene-III

  摘要：

  The monoalcohols (-)-globulol (2), (-)-epiglobulol (3), (-)-ledol (4), and (+)-viridiflorol (5) were synthesized from (+)-aromadendrene (1). The cis-fused alloaromadendrone (14), the key intermediate used in the synthesis of 4 and 5, was obtained from the trans-fused apoaromadendrone (13) via a selective protonation of the thermodynamic enol trimethylsilylether 15. After hydroxylation of the tertiary C11 of 13 with RuO4, (+)-spathulenol (6), (-)-allospathulenol (7), and the aromadendrane diols 8-11 could be prepared. Compounds 2-11 were tested for antifungal properties, but their activity was only moderate.

  DOI：

  10.1016/s0040-4020(01)88765-2

文献信息

• Base-induced and -directed elimination and rearrangement of perhydronaphthalene-1,4-diol monosulfonate esters. Total synthesis of (.+-.)-alloaromadendrane-4.beta.,10.alpha.-diol and (.+-.)-alloaromadendrane-4.alpha.,10.alpha.-diol
  作者：Louis H. D. Jenniskens、Joannes B. P. A. Wijnberg、Aede De Groot

  DOI：10.1021/jo00023a025

  日期：1991.11

  The total synthesis of (+/-)-alloaromadendrane-4-beta,10-alpha-diol (1), supposedly isolated from Ambrosia peruviana Willd., is described. The strategically positioned axial hydroxyl group at C(4) played a crucial role in the two key steps of this synthesis (2 and 11 --> 3; 4 --> 5). Upon treatment with sodium tert-amylate in refluxing toluene, both the mesylates 2 and 11 predominantly gave the olefin 3. A mechanism for this regioselective elimination is proposed. The double bond of 3 at C(6)-C(7) was used to introduce a dimethylcyclopropane ring at this position. The intramolecular base-induced rearrangement of 4 proceeded with high selectivity, again guided by the alkoxide at C(4). The resulting exo olefin 5 was converted into diol 1, but its spectral data did not agree with those reported for the natural diol. The epimeric (+/-)-alloaromadendrane-4-alpha,10-alpha-diol (23) was prepared from 5 via a dehydratation, epoxidation, reduction sequence. Now the spectral data of the natural and the synthetic diol agreed very well and a revision of the structure of the natural product is postulated.
• The synthesis of mono- and dihydroxy aromadendrane sesquiterpenes, starting from natural (+)-aromadendrene-III
  作者：Harrie J.M. Gijsen、Joannes B.P.A. Wijnberg、Gerrit A. Stork、Aede de Groot、Maarten A. de Waard、Johannes G.M. van Nistelrooy

  DOI：10.1016/s0040-4020(01)88765-2

  日期：1992.3

  The monoalcohols (-)-globulol (2), (-)-epiglobulol (3), (-)-ledol (4), and (+)-viridiflorol (5) were synthesized from (+)-aromadendrene (1). The cis-fused alloaromadendrone (14), the key intermediate used in the synthesis of 4 and 5, was obtained from the trans-fused apoaromadendrone (13) via a selective protonation of the thermodynamic enol trimethylsilylether 15. After hydroxylation of the tertiary C11 of 13 with RuO4, (+)-spathulenol (6), (-)-allospathulenol (7), and the aromadendrane diols 8-11 could be prepared. Compounds 2-11 were tested for antifungal properties, but their activity was only moderate.