(2R,3S)-1,3-O-benzylidene-1,2,3-octadecanetriol-4-one | 150162-78-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (2R,3S)-1,3-O-benzylidene-1,2,3-octadecanetriol-4-one
• 英文别名: 1,3-O-benzylidene-1,2,3-octadecanetriol-4-one；1-[(2S,4S,5R)-5-hydroxy-2-phenyl-1,3-dioxan-4-yl]pentadecan-1-one
• CAS: 150162-78-0
• 化学式: C₂₅H₄₀O₄
• 分子量: 404.59
• InChiKey: LWLGBZWZVYMEQN-SDHSZQHLSA-N

物化性质

• 沸点：
  542.9±50.0 °C(Predicted)
• 密度：
  1.022±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  29
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 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：

  (2R,3S)-1,3-O-benzylidene-1,2,3-octadecanetriol-4-one 在 吡啶 、 sodium azide 、 三氟化硼乙醚 、 硫化氢 、 水 、 L-Selectride 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 52.0h， 生成 糖脂
  参考文献：
  名称：

  Sphingosine and phytosphingosine from D-threose synthesis of a 4-keto-ceramide

  摘要：

  Reaction of 2,4-O-benzylidene-D-threose 3 with tetradecyl magnesium bromide furnished D-arabino- and L-xylo-octadecane-1,2,3,4-tetrols 5a,x. Regioselective oxidation of the 4-OH group gave 4-keto-D-erythro-derivative 6 which can be reduced with acetaldehyde in a SmI2-catalyzed Tishtshenko reaction to afford exclusively 5a. Regioselective 2-O-mesylation of 5a (--> 7a) and then acid catalyzed debenzylation afforded exclusively 2-O-mesyl-tetrol 9a. Reaction with NaN3 and ensuing azide reduction furnished D-ribo-C-18-phytosphingosine (2) in high overall yield. Treatment of 2-O-mesyl derivatives 7a,x with NaN3 and then with 4-nitrobenzenesulfonyl chloride in pyridine afforded 11r,l. Elimination with DBU or, alternatively, by treatment with phenylselenide and then with H2O2, gave known 1,3-O-benzylidene protected azidosphingosine 14, which can be readily converted into sphingosine (1). Transformation of 2 into ceramide 15, selective 1,3-O-silyl protection, oxidation of the 4-OH group (--> 17) and then desilylation afforded the 4-keto ceramide 18 found in a marine sponge. Reduction of 17 offers a convenient possibility for radioactive labelling of ceramides with tritium.

  DOI：

  10.1016/s0957-4166(00)86295-3
• 作为产物：
  描述：

  2,4-O-benzylidene-D-threose 在 重铬酸吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (2R,3S)-1,3-O-benzylidene-1,2,3-octadecanetriol-4-one
  参考文献：
  名称：

  Baer, Thomas; Kratzer, Bernd; Wild, Robert, Liebigs Annalen der Chemie, 1993, # 4, p. 419 - 426

  摘要：

  DOI：

文献信息

• Sphingosine and phytosphingosine from D-threose synthesis of a 4-keto-ceramide
  作者：Robert Wild、Richard R. Schmidt

  DOI：10.1016/s0957-4166(00)86295-3

  日期：1994.11

  Reaction of 2,4-O-benzylidene-D-threose 3 with tetradecyl magnesium bromide furnished D-arabino- and L-xylo-octadecane-1,2,3,4-tetrols 5a,x. Regioselective oxidation of the 4-OH group gave 4-keto-D-erythro-derivative 6 which can be reduced with acetaldehyde in a SmI2-catalyzed Tishtshenko reaction to afford exclusively 5a. Regioselective 2-O-mesylation of 5a (--> 7a) and then acid catalyzed debenzylation afforded exclusively 2-O-mesyl-tetrol 9a. Reaction with NaN3 and ensuing azide reduction furnished D-ribo-C-18-phytosphingosine (2) in high overall yield. Treatment of 2-O-mesyl derivatives 7a,x with NaN3 and then with 4-nitrobenzenesulfonyl chloride in pyridine afforded 11r,l. Elimination with DBU or, alternatively, by treatment with phenylselenide and then with H2O2, gave known 1,3-O-benzylidene protected azidosphingosine 14, which can be readily converted into sphingosine (1). Transformation of 2 into ceramide 15, selective 1,3-O-silyl protection, oxidation of the 4-OH group (--> 17) and then desilylation afforded the 4-keto ceramide 18 found in a marine sponge. Reduction of 17 offers a convenient possibility for radioactive labelling of ceramides with tritium.
• Baer, Thomas; Kratzer, Bernd; Wild, Robert, Liebigs Annalen der Chemie, 1993, # 4, p. 419 - 426
  作者：Baer, Thomas、Kratzer, Bernd、Wild, Robert、Sandhoff, Konrad、Schmidt, Richard R.

  DOI：——

  日期：——