ethyl (1R*,6S*,8aS*)-1,6-dimethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene-4-carboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (1R*,6S*,8aS*)-1,6-dimethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene-4-carboxylate
• 英文别名: ethyl (4S,4aR,7R)-4,7-dimethyl-2,3,4,4a,5,6,7,8-octahydronaphthalene-1-carboxylate
• 化学式: C₁₅H₂₄O₂
• 分子量: 236.354
• InChiKey: BQJFCWCPAQMDTD-GRYCIOLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl (1R*,6S*,8aS*)-1,6-dimethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene-4-carboxylate 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 6.0h， 以95%的产率得到ethyl (1R*,4R*,4aS*,6S*,8aS*)-1,2,3,4,4a,5,6,7,8,8a-decahydro-1,6-dimethylnaphthalene-4-carboxylate
  参考文献：
  名称：

  Intramolecular Ene Reaction of Vinylphosphonates. Synthetic Application to Bicyclic Compounds and Cadalane and Valerenic Acid Terpenoids

  摘要：

  The Lewis-acid-catalyzed intramolecular ene-reaction of vinylphosphonates 4, 6, and 7, prepared by the Knoevenagel condensation of triethyl phosphonoacetate (3) with citronellal (1) or 2,6-dimethyl-5-heptenal(2), stereoselectively gave 2-(8'-p-menthen-3'-yl) or 2-(2'-isopropenyl-5'-methylcyclopent-1'-yl)phosphonoacetates 8-10 in high yields. The Wittig-Horner reaction of the phosphonates 8-10 with paraformaldehyde led to 1,5-diene compounds 12a,b and 13b in 87-90% yield. Subsequent Lewis-acid-catalyzed cyclization of the compounds 12, 13 or 25, 27 afforded 1,6-dimethyloctahydronaphthalene-4-carboxylates 17, 22, or carbaldehydes 28, 29 and/or 8-methyl-2,5-dimethylenebicyclo[4.4.0]decan-4-ol (30). Palladium-catalyzed metallo-ene reaction of the acetate 32 afforded 2,5,8-trimethyl-1,2,3,4-tetrahydronaphthalene (34). The bicyclic compounds 17a and 29 were applied to the synthesis of cadalane and valerenic acid sesquiterpenoids.

  DOI：

  10.1021/jo00101a034
• 作为产物：
  描述：

  香茅醛 在 哌啶 二氯乙基铝 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 45.0h， 生成 ethyl (1R*,6S*,8aS*)-1,6-dimethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene-4-carboxylate
  参考文献：
  名称：

  Intramolecular Ene Reaction of Vinylphosphonates. Synthetic Application to Bicyclic Compounds and Cadalane and Valerenic Acid Terpenoids

  摘要：

  The Lewis-acid-catalyzed intramolecular ene-reaction of vinylphosphonates 4, 6, and 7, prepared by the Knoevenagel condensation of triethyl phosphonoacetate (3) with citronellal (1) or 2,6-dimethyl-5-heptenal(2), stereoselectively gave 2-(8'-p-menthen-3'-yl) or 2-(2'-isopropenyl-5'-methylcyclopent-1'-yl)phosphonoacetates 8-10 in high yields. The Wittig-Horner reaction of the phosphonates 8-10 with paraformaldehyde led to 1,5-diene compounds 12a,b and 13b in 87-90% yield. Subsequent Lewis-acid-catalyzed cyclization of the compounds 12, 13 or 25, 27 afforded 1,6-dimethyloctahydronaphthalene-4-carboxylates 17, 22, or carbaldehydes 28, 29 and/or 8-methyl-2,5-dimethylenebicyclo[4.4.0]decan-4-ol (30). Palladium-catalyzed metallo-ene reaction of the acetate 32 afforded 2,5,8-trimethyl-1,2,3,4-tetrahydronaphthalene (34). The bicyclic compounds 17a and 29 were applied to the synthesis of cadalane and valerenic acid sesquiterpenoids.

  DOI：

  10.1021/jo00101a034