ethyl (E)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate | 160715-83-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: ethyl (E)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate
• 英文别名: ethyl (2E)-2-diethoxyphosphoryl-5,9-dimethyldeca-2,8-dienoate
• CAS: 160715-83-3
• 化学式: C₁₈H₃₃O₅P
• 分子量: 360.431
• InChiKey: PAZGKZFWHWURPG-SAPNQHFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (E)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate 在 二氯乙基铝 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以80%的产率得到ethyl (2S*,1'S*,3'S*,4'S*)-2-(diethoxyphosphinyl)-2-(8'-p-menthen-3'-yl)acetate
  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：

  磷酰基乙酸三乙酯 、 香茅醛 在 哌啶 作用下， 以 乙醇 为溶剂， 反应 30.0h， 以35.5%的产率得到ethyl (E)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate
  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