(1α,4α,4aα,7β,8aβ)-5-<(tert-butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalene-diol 7-(methanesulfonate) | 136379-61-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (1α,4α,4aα,7β,8aβ)-5-<(tert-butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalene-diol 7-(methanesulfonate)
• 英文别名: (1α,4α,4aα,7β,8aβ)-4-<(tert-Butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalenediol 7-(methanesulfonate)；[(2R,4aS,5S,8R,8aS)-5-[tert-butyl(dimethyl)silyl]oxy-8-hydroxy-4a,8-dimethyl-1,2,3,4,5,6,7,8a-octahydronaphthalen-2-yl] methanesulfonate
• CAS: 136379-61-8
• 化学式: C₁₉H₃₈O₅SSi
• 分子量: 406.659
• InChiKey: DKSQDFQMUZQVFI-NLPXPOPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  81.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1α,4α,4aα,7β,8aβ)-5-<(tert-butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalene-diol 7-(methanesulfonate) 在 15-冠醚-5 、 sodium tert-pentoxide 作用下， 以 甲苯 、 苯 为溶剂， 反应 0.17h， 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 、 (1α,4α,4aα,8aβ)-4-<(tert-Butyldimethylsilyl)oxy>-1,2,3,4,4a,5,8,8a-octahydro-1,4a-dimethyl-1-naphthalenol
  参考文献：
  名称：

  Intramolecular alkoxide induced heterolysis of perhydronaphthalene-1,4-diol monosulfonate esters through orbital interactions over three carbon-carbon single bonds

  摘要：

  The course of the reactions that occur when stereochemically rigid trans-perhydronaphthalene-1,4-diol monosulfonate esters (1-4) are treated with alkali metal tert-amylate in refluxing benzene depends on the relative orientation of the leaving group and the tertiary hydroxyl group. An equatorial sulfonate ester group favors homofragmentation leading to the cyclopropane derivative 15. In case of an axial sulfonate ester group beta-elimination, which strongly depends on the stereochemistry of the tertiary deprotonated hydroxyl group, is the main reaction path. The 0-silylated mesylates 5 and 6 show no reaction at all upon treatment with strong base; fast reactions are observed when 5 and 6 are treated with TBAF. Generation of an alcoholate is crucial for the observed reactions. Homofragmentation and an internal return reaction with inversion of configuration of the mesylate group in the axial mesylates 1 and 3 is explained by assuming a stabilized 1,3-bridged intermediate carbocation. This also explains why the equatorial mesylates react slightly faster than the axial mesylates. The reactivity of the alpha-mesylates is controlled by through-bond induction alone, whereas the reactivity of the corresponding beta-mesylates is determined by the sum of a through-bond and a through-space (1,3-bridging) interaction.

  DOI：

  10.1021/jo00057a037
• 作为产物：
  描述：

  (4α,4aα,8aβ)-4-[(tert-Butyldimethylsilyl)oxy]octahydro-7,7-dimethoxy-4a-methyl-1(2H)-naphthalenone 在 吡啶 、 盐酸 、 L-Selectride 作用下， 以 乙醚 、 水 、 丙酮 为溶剂， 反应 44.33h， 生成 (1α,4α,4aα,7β,8aβ)-5-<(tert-butyldimethylsilyl)oxy>decahydro-1,4a-dimethyl-1,7-naphthalene-diol 7-(methanesulfonate)
  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.
• Intramolecular alkoxide induced heterolysis of perhydronaphthalene-1,4-diol monosulfonate esters through orbital interactions over three carbon-carbon single bonds
  作者：Romano V. A. Orru、Joannes B. P. A. Wijnberg、Louis H. D. Jenniskens、Aede De Groot

  DOI：10.1021/jo00057a037

  日期：1993.2

  The course of the reactions that occur when stereochemically rigid trans-perhydronaphthalene-1,4-diol monosulfonate esters (1-4) are treated with alkali metal tert-amylate in refluxing benzene depends on the relative orientation of the leaving group and the tertiary hydroxyl group. An equatorial sulfonate ester group favors homofragmentation leading to the cyclopropane derivative 15. In case of an axial sulfonate ester group beta-elimination, which strongly depends on the stereochemistry of the tertiary deprotonated hydroxyl group, is the main reaction path. The 0-silylated mesylates 5 and 6 show no reaction at all upon treatment with strong base; fast reactions are observed when 5 and 6 are treated with TBAF. Generation of an alcoholate is crucial for the observed reactions. Homofragmentation and an internal return reaction with inversion of configuration of the mesylate group in the axial mesylates 1 and 3 is explained by assuming a stabilized 1,3-bridged intermediate carbocation. This also explains why the equatorial mesylates react slightly faster than the axial mesylates. The reactivity of the alpha-mesylates is controlled by through-bond induction alone, whereas the reactivity of the corresponding beta-mesylates is determined by the sum of a through-bond and a through-space (1,3-bridging) interaction.