(1R,4S,4aS,8aS)-4-(tert-Butyl-dimethyl-silanyloxy)-7,7-dimethoxy-1,4a-dimethyl-decahydro-naphthalen-1-ol | 144494-49-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4S,4aS,8aS)-4-(tert-Butyl-dimethyl-silanyloxy)-7,7-dimethoxy-1,4a-dimethyl-decahydro-naphthalen-1-ol
• CAS: 144494-49-5
• 化学式: C₂₀H₄₀O₄Si
• 分子量: 372.621
• InChiKey: GZCFRRXRKJTPDZ-PBWTXFEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.72
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1R,4S,4aS,8aS)-4-(tert-Butyl-dimethyl-silanyloxy)-7,7-dimethoxy-1,4a-dimethyl-decahydro-naphthalen-1-ol 在 吡啶 、 盐酸 、 sodium tert-pentoxide 、 L-Selectride 作用下， 以 水 、 丙酮 、 甲苯 为溶剂， 反应 2.5h， 生成 (1R,4S,4aS,8aS)-4-{[叔-丁基(二甲基)甲硅烷基]氧代}-1,4a-二甲基-1,2,3,4,4a,5,6,8a-八氢萘-1-酚
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00023a025
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 114.0h， 生成 (1R,4S,4aS,8aS)-4-(tert-Butyl-dimethyl-silanyloxy)-7,7-dimethoxy-1,4a-dimethyl-decahydro-naphthalen-1-ol
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00023a025