(1α,4α,4aα,7α,8aβ)-4-<(tert-Butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalenediol | 136379-67-4

• 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: (1α,4α,4aα,7α,8aβ)-4-<(tert-Butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalenediol
• 英文别名: (1R,4S,4aS,7S,8aS)-4-(tert-Butyldimethylsilyl)oxy-1,4a-dimethyl-2,3,4,5,6,7,8,8a-octahydronaphthalene-1,7-diol；(1R,4S,4aS,7S,8aS)-4-[tert-butyl(dimethyl)silyl]oxy-1,4a-dimethyl-2,3,4,5,6,7,8,8a-octahydronaphthalene-1,7-diol
• CAS: 136379-67-4
• 化学式: C₁₈H₃₆O₃Si
• 分子量: 328.568
• InChiKey: IFOFSNZZMMDDRH-FTAMUGHTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.09
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 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 、 sodium tetrahydroborate 作用下， 以 乙醚 、 水 、 丙酮 为溶剂， 反应 42.33h， 生成 (1α,4α,4aα,7α,8aβ)-4-<(tert-Butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalenediol
  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.