isopropyl (Z)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate | 160715-86-6

• 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: isopropyl (Z)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate
• 英文别名: propan-2-yl (2Z)-2-diethoxyphosphoryl-5,9-dimethyldeca-2,8-dienoate
• CAS: 160715-86-6
• 化学式: C₁₉H₃₅O₅P
• 分子量: 374.458
• InChiKey: ISKGLLYPRUDJEV-JXAWBTAJSA-N

物化性质

• 沸点：
  458.1±45.0 °C(Predicted)
• 密度：
  1.011±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  25
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.74
• 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：

  isopropyl (Z)-2-(diethoxyphosphinyl)-5,9-dimethyldeca-2,8-dienoate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 吡啶 、 4-二甲氨基吡啶 、 sodium hydride 、 二异丁基氢化铝 、 三苯基膦 、 zinc dibromide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 23.75h， 生成 2,5,8-三甲基-1,2,3,4-四氢萘
  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 、 chlorotitanium(IV) triisopropoxide 在 sodium hydride 作用下， 生成 isopropyl (Z)-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

文献信息

• Intramolecular Ene Reaction of Vinylphosphonates. Synthetic Application to Bicyclic Compounds and Cadalane and Valerenic Acid Terpenoids
  作者：Toru Minami、Tomohisa Utsunomiya、Seigo Nakamura、Michiharu Okubo、Naotaka Kitamura、Yoshiharu Okada、Junji Ichikawa

  DOI：10.1021/jo00101a034

  日期：1994.11

  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.