4β-Hydroxy-4aβ-methyl-3,4,4a,5,6,8aα-hexahydronaphthalene-1(2H),7(8H)-dione 7-dimethyl acetal | 87262-05-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4β-Hydroxy-4aβ-methyl-3,4,4a,5,6,8aα-hexahydronaphthalene-1(2H),7(8H)-dione 7-dimethyl acetal
• 英文别名: 1(2H)-Naphthalenone, octahydro-4-hydroxy-7,7-dimethoxy-4a-methyl-, (4alpha,4aalpha,8abeta)-；(4S,4aS,8aS)-4-hydroxy-7,7-dimethoxy-4a-methyl-3,4,5,6,8,8a-hexahydro-2H-naphthalen-1-one
• CAS: 87262-05-3
• 化学式: C₁₃H₂₂O₄
• 分子量: 242.315
• InChiKey: VFCAWEZEUPDVLT-USWWRNFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4β-Hydroxy-4aβ-methyl-3,4,4a,5,6,8aα-hexahydronaphthalene-1(2H),7(8H)-dione 7-dimethyl acetal 在 platinum on activated charcoal 盐酸 、 氢气 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 、 二甲基亚砜 为溶剂， 25.0~55.0 ℃ 、344.73 kPa 条件下， 反应 80.92h， 生成 (1α,4α,4aα,7α,8aβ)-decahydro-1,4a-dimethyl-7-(1-methylethyl)-1,4-naphthalenediol
  参考文献：
  名称：

  Base-induced and -directed rearrangements of 4-monotosylated perhydronaphthalene-1,4-diols. Synthesis of (.+-.)-5-epi-nardol

  摘要：

  DOI：

  10.1021/jo00290a027
• 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 氢溴酸 、 sodium methylate 、 对甲苯磺酸 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 50.75h， 生成 4β-Hydroxy-4aβ-methyl-3,4,4a,5,6,8aα-hexahydronaphthalene-1(2H),7(8H)-dione 7-dimethyl acetal
  参考文献：
  名称：

  Stereospecific synthesis of selectively C-7-acetalized substituted 4a.beta.-methyl-3,4,4a,5,6,8a.alpha.-hexahydronaphthalene-1(2H),7(8H)-diones. A short total synthesis of (.+-.)-.beta.-eudesmol, (.+-.)-.beta.-selinene, and (.+-.)-.beta.-dictyopterol

  摘要：

  DOI：

  10.1021/jo00171a045

文献信息

• A selective base-induced rearrangement of perhydronaphthalenes to 1,5-cis-fused 10-methylene perhydroazulenes
  作者：Joannes B.P.A. Wijnberg、Ae. de Groot

  DOI：10.1016/s0040-4039(00)96269-5

  日期：——

  The rearrangement of perhydronaphthalenic tosylate 3 to 1,5-cis 10-methylene perhydroazulene 4 was achieved selectively and in high yield via intramolecular assistance of a 4β hydroxylate.

  通过4β羟基化物的分子内辅助，选择性地并且高收率地实现了全氢萘基甲苯磺酸酯3到1，5-顺式10-亚甲基全氢祖烯4的重排。
• 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.
• 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.