(4α,4aα,8aβ)-4-[(tert-Butyldimethylsilyl)oxy]octahydro-7,7-dimethoxy-4a-methyl-1(2H)-naphthalenone | 136379-64-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4α,4aα,8aβ)-4-[(tert-Butyldimethylsilyl)oxy]octahydro-7,7-dimethoxy-4a-methyl-1(2H)-naphthalenone
• 英文别名: (4S,4aS,8aS)-4-[tert-butyl(dimethyl)silyl]oxy-7,7-dimethoxy-4a-methyl-3,4,5,6,8,8a-hexahydro-2H-naphthalen-1-one
• CAS: 136379-64-1
• 化学式: C₁₉H₃₆O₄Si
• 分子量: 356.578
• InChiKey: IIQJRZFDGHTZOK-HFTRVMKXSA-N

物化性质

• 沸点：
  383.1±42.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4α,4aα,8aβ)-4-[(tert-Butyldimethylsilyl)oxy]octahydro-7,7-dimethoxy-4a-methyl-1(2H)-naphthalenone 在 吡啶 、 盐酸 、 lithium aluminium tetrahydride 、 (dimethylsulfinyl)sodium 、 sodium tert-pentoxide 、 对甲苯磺酸 、 magnesium monoperoxyphthalate hexahydrate 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 丙酮 、 甲苯 、 苯 为溶剂， 反应 45.92h， 生成 (1α,4β,4aβ,8aα)-4-<(tert-butyldimethylsilyl)oxy>-1,2,3,4,4a,5,6,8a-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：

  acetic acid (1S*,8aS*)-(+/-)-8a-methyl-6-oxo-1,2,3,4,6,7,8,8a-octahydronaphthalen-1-yl ester 在 咪唑 、 Oxone 、 三甲基氯硅烷 、 氢溴酸 、 对甲苯磺酸 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (4α,4aα,8aβ)-4-[(tert-Butyldimethylsilyl)oxy]octahydro-7,7-dimethoxy-4a-methyl-1(2H)-naphthalenone
  参考文献：
  名称：

  Synthesis of (E,E)-Germacrane Sesquiterpene Alcohols via Enolate-Assisted 1,4-Fragmentation

  摘要：

  An efficient method has been developed for the synthesis of (E,E)-germacrane sesquiterpene alcohols, The key step in these syntheses involves the enolate-assisted 1,4-fragmentation of properly functionalized perhydro-1-naphthalenecarboxaldehydes with 1 equiv of sodium tert-amylate as base, to give the corresponding (E,E)-germacrane aldehydes. These aldehydes are not very stable, and in situ reduction of the aldehyde function with Red-Al is required to obtain high yields of the desired germacrane alcohols. This procedure has led to the successful synthesis of 15-hydroxygermacrene B (4) and 15-hydroxyhedycaryol (35) from the mesylates 6 and 33, respectively. When KHMDS is used instead of sodium tert-amylate in the fragmentation reaction of 6, isomerization of the initially formed C(4)-C(5) E double bond cannot be avoided and results, after in situ reduction with Red-Al, in the formation of the (E,Z)-germacrane alcohol 24. The 15-hydroxg-(E,E)-germacranes are excellent starting materials for the selective synthesis of the corresponding 4,5-epoxides, which in turn can perfectly well be used in studies on the biomimetic formation of guaiane sesquiterpenes.

  DOI：

  10.1021/jo970901z

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.
• Synthesis of (<i>E</i>,<i>E</i>)-Germacrane Sesquiterpene Alcohols via Enolate-Assisted 1,4-Fragmentation
  作者：Adriaan J. Minnaard、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo970901z

  日期：1997.10.1

  An efficient method has been developed for the synthesis of (E,E)-germacrane sesquiterpene alcohols, The key step in these syntheses involves the enolate-assisted 1,4-fragmentation of properly functionalized perhydro-1-naphthalenecarboxaldehydes with 1 equiv of sodium tert-amylate as base, to give the corresponding (E,E)-germacrane aldehydes. These aldehydes are not very stable, and in situ reduction of the aldehyde function with Red-Al is required to obtain high yields of the desired germacrane alcohols. This procedure has led to the successful synthesis of 15-hydroxygermacrene B (4) and 15-hydroxyhedycaryol (35) from the mesylates 6 and 33, respectively. When KHMDS is used instead of sodium tert-amylate in the fragmentation reaction of 6, isomerization of the initially formed C(4)-C(5) E double bond cannot be avoided and results, after in situ reduction with Red-Al, in the formation of the (E,Z)-germacrane alcohol 24. The 15-hydroxg-(E,E)-germacranes are excellent starting materials for the selective synthesis of the corresponding 4,5-epoxides, which in turn can perfectly well be used in studies on the biomimetic formation of guaiane sesquiterpenes.