(1aα,3aα,4α,7α,7aβ,7bα)-1,1-Dibromo-4-<(tert-butyldimethylsilyl)oxy>decahydro-3a,7-dimethyl-1H-cyclopropanaphthalen-7-ol | 136379-70-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1aα,3aα,4α,7α,7aβ,7bα)-1,1-Dibromo-4-<(tert-butyldimethylsilyl)oxy>decahydro-3a,7-dimethyl-1H-cyclopropanaphthalen-7-ol
• 英文别名: (1aα,3aα,4α,7α,7aβ,7bα)-1,1-Dibromo-4-[(tert-butyldimethylsilyl)oxy]decahydro-3a,7-dimethyl-1H-cyclopropa[a]naphthalen-7-ol；1H-Cyclopropa(a)naphthalen-7-ol, 1,1-dibromo-4-(((1,1-dimethylethyl)dimethylsilyl)oxy)decahydro-3a,7-dimethyl-, (1aalpha,3aalpha,4alpha,7alpha,7abeta,7balpha)-；(1aR,3aS,4S,7R,7aS,7bS)-1,1-dibromo-4-[tert-butyl(dimethyl)silyl]oxy-3a,7-dimethyl-1a,2,3,4,5,6,7a,7b-octahydrocyclopropa[a]naphthalen-7-ol
• CAS: 136379-70-9
• 化学式: C₁₉H₃₄Br₂O₂Si
• 分子量: 482.371
• InChiKey: VEXUEDHKPHIZDP-VXNIPGDTSA-N

物化性质

• 沸点：
  429.9±45.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.07
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

SDS

反应信息

• 作为反应物：
  描述：

  甲基锂 、 (1aα,3aα,4α,7α,7aβ,7bα)-1,1-Dibromo-4-<(tert-butyldimethylsilyl)oxy>decahydro-3a,7-dimethyl-1H-cyclopropanaphthalen-7-ol 、 (lithium)2(CN)(methyl)2cuprate 在 六甲基磷酰三胺 作用下， 生成 (1aR,3aS,4S,7R,7aS,7bR)-4-{[叔-丁基(二甲基)甲硅烷基]氧代}-1,1,3a,7-四甲基十氢-1H-环丙烯并[a]萘-7-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：

  (4α,4aα,8aβ)-4-[(tert-Butyldimethylsilyl)oxy]octahydro-7,7-dimethoxy-4a-methyl-1(2H)-naphthalenone 在 盐酸 作用下， 以 乙醚 、 水 、 丙酮 为溶剂， 反应 42.33h， 生成 (1aα,3aα,4α,7α,7aβ,7bα)-1,1-Dibromo-4-<(tert-butyldimethylsilyl)oxy>decahydro-3a,7-dimethyl-1H-cyclopropanaphthalen-7-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

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.