(1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo<3.2.1>octane | 143669-25-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧环庚烷
• 英文名称: (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo<3.2.1>octane
• 英文别名: (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane
• CAS: 143669-25-4
• 化学式: C₂₂H₄₂O₃
• 分子量: 354.574
• InChiKey: JTLKNFDMCVWVIR-FSSWDIPSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  25
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo<3.2.1>octane 在 lithium aluminium tetrahydride 、 三氯化铝 作用下， 以 乙醚 为溶剂， 以73%的产率得到(2S,5S)-5-heptadecyl-2-(hydroxymethyl)-1,4-dioxane
  参考文献：
  名称：

  Syntheses of all four stereoisomers which are conformationally constrained 1,4-dioxanyl analogs of the antineoplastic ether lipid ET-18-OCH3

  摘要：

  The syntheses of each of the four nearly optically pure stereoisomers of [[(5-heptadecyl-1,4-dioxan-2-yl)-methyl]oxy]phosphocholine (2,3,2',3') were performed by two parallel divergent sequences. Phosphocholines 2 and 3 were prepared via the corresponding 5-heptadecyl-2-(hydroxymethyl)-1,4-dioxanes 21 and 23, respectively, from the completely regiospecific mixed-hydride reductions of (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (19) and (1R,4R,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (20), respectively. The two 4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octanes 19 and 20 were the two separable products from an intramolecular cyclization reaction. By a parallel divergent sequence from the enantiomeric starting material, 3-O-benzyl-sn-glycerol (16'), the other two diastereomeric [[(5-heptadecyl-1,4-dioxan-2-yl)methyl]oxy]phosphocholines 2' and 3' were prepared. These four monocyclic [[(5-heptadecyl-1,4-dioxan-2-yl)methyl]oxy]phosphocholines (2,3,2',3') are conformationally constrained analogs of the antineoplastic and immunomodulatory ether lipid rac-2-O-methyl-1-O-octadecylglycero-3-phosphocholine (rac-1) (rac-ET-18-OCH3, rac-Edelfosine).

  DOI：

  10.1021/jo00049a021
• 作为产物：
  描述：

  2-bromo-1,1-dimethoxynonadecane 在 palladium dihydroxide potassium tert-butylate 、 氢气 、 对甲苯磺酸 作用下， 以 甲醇 、 叔丁醇 为溶剂， 65.0~100.0 ℃ 、344.73 kPa 条件下， 反应 24.0h， 生成 (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo<3.2.1>octane
  参考文献：
  名称：

  Syntheses of all four stereoisomers which are conformationally constrained 1,4-dioxanyl analogs of the antineoplastic ether lipid ET-18-OCH3

  摘要：

  The syntheses of each of the four nearly optically pure stereoisomers of [[(5-heptadecyl-1,4-dioxan-2-yl)-methyl]oxy]phosphocholine (2,3,2',3') were performed by two parallel divergent sequences. Phosphocholines 2 and 3 were prepared via the corresponding 5-heptadecyl-2-(hydroxymethyl)-1,4-dioxanes 21 and 23, respectively, from the completely regiospecific mixed-hydride reductions of (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (19) and (1R,4R,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (20), respectively. The two 4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octanes 19 and 20 were the two separable products from an intramolecular cyclization reaction. By a parallel divergent sequence from the enantiomeric starting material, 3-O-benzyl-sn-glycerol (16'), the other two diastereomeric [[(5-heptadecyl-1,4-dioxan-2-yl)methyl]oxy]phosphocholines 2' and 3' were prepared. These four monocyclic [[(5-heptadecyl-1,4-dioxan-2-yl)methyl]oxy]phosphocholines (2,3,2',3') are conformationally constrained analogs of the antineoplastic and immunomodulatory ether lipid rac-2-O-methyl-1-O-octadecylglycero-3-phosphocholine (rac-1) (rac-ET-18-OCH3, rac-Edelfosine).

  DOI：

  10.1021/jo00049a021

文献信息

• Single crystal X-ray structures of the two 4-heptadecyl derivatives of (1R,5S)-3,6,8-trioxabicylo[3.2.1]octane
  作者：Jill Moring、Richard I. Duclos、Jian-Hua Zhang、Leo G. Herbette、Xiangqun Xie、Alexandros Makriyannis

  DOI：10.1016/0009-3084(95)02458-u

  日期：1995.8

  The single crystal structures of the two diastereomeric 4-heptadecyl derivatives of (1R,5S)-3,6,8-trioxabicyclo[3.2.1]octane have been determined by X-ray diffraction to be (1R,4R,5S)-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (I) and (1R,4S,5S)-4-heptadecyl[3,6,8-trioxabicyclo[3.2.1]octane (II), respectively, which have an exo or axial 4-heptadecyl group, and an endo or equatorial 4-heptadecyl group

  （1R，5S）-3,6,8-三氧杂双环[3.2.1]辛烷的两个非对映体4-十七烷基衍生物的单晶结构已通过X射线衍射确定为（1R，4R，5S）-七癸基-3,6,8-三氧杂双环[3.2.1]辛烷（I）和（1R，4S，5S）-4-十七烷基[3,6,8-三氧杂双环[3.2.1]辛烷（II），它们分别具有外或轴向的4-十七烷基和内或赤道的4-十七烷基。I和II的结构已通过其相敏2D NOESY 1H-NMR光谱提出，但现在已明确建立。这些光学纯的非离子脂质样两亲分子（I和II）代表已解决单晶结构的前3,6,8-三氧杂双环[3.2.1]辛烷。异构体I和异构体II的晶体均为正交晶体，空间群为P2（1）2（1）2（1），且其晶胞尺寸分别为a = 9.586，b = 43.14，c = 5.289 A和a = 7.34，b = 51.8，c = 5.636A。I和II的结构均通过直接方法分别求解为R = 0
• Syntheses of all four stereoisomers which are conformationally constrained 1,4-dioxanyl analogs of the antineoplastic ether lipid ET-18-OCH3
  作者：Richard I. Duclos、Alexandros Makriyannis

  DOI：10.1021/jo00049a021

  日期：1992.11

  The syntheses of each of the four nearly optically pure stereoisomers of [[(5-heptadecyl-1,4-dioxan-2-yl)-methyl]oxy]phosphocholine (2,3,2',3') were performed by two parallel divergent sequences. Phosphocholines 2 and 3 were prepared via the corresponding 5-heptadecyl-2-(hydroxymethyl)-1,4-dioxanes 21 and 23, respectively, from the completely regiospecific mixed-hydride reductions of (1R,4S,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (19) and (1R,4R,5S)-4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octane (20), respectively. The two 4-heptadecyl-3,6,8-trioxabicyclo[3.2.1]octanes 19 and 20 were the two separable products from an intramolecular cyclization reaction. By a parallel divergent sequence from the enantiomeric starting material, 3-O-benzyl-sn-glycerol (16'), the other two diastereomeric [[(5-heptadecyl-1,4-dioxan-2-yl)methyl]oxy]phosphocholines 2' and 3' were prepared. These four monocyclic [[(5-heptadecyl-1,4-dioxan-2-yl)methyl]oxy]phosphocholines (2,3,2',3') are conformationally constrained analogs of the antineoplastic and immunomodulatory ether lipid rac-2-O-methyl-1-O-octadecylglycero-3-phosphocholine (rac-1) (rac-ET-18-OCH3, rac-Edelfosine).