Methyl (4S,5S,15S)-4,5,15,16-tetrahydroxyhexadec-2-enoate bis-acetonide | 153915-88-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl (4S,5S,15S)-4,5,15,16-tetrahydroxyhexadec-2-enoate bis-acetonide
• 英文别名: methyl (E)-3-[(4S,5S)-5-[9-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]nonyl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• CAS: 153915-88-9
• 化学式: C₂₃H₄₀O₆
• 分子量: 412.567
• InChiKey: XOCXXLJHADGROD-OSAQNZNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  29
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Methyl (4S,5S,15S)-4,5,15,16-tetrahydroxyhexadec-2-enoate bis-acetonide 在 偶氮二异丁腈 4-二甲氨基吡啶 、 lithium hydroxide 、 三正丁基氢锡 、 4-甲基苯磺酸吡啶 、 原乙酸三乙酯 、 三乙胺 作用下， 以 四氢呋喃 、 溶剂黄146 、 甲苯 、 苯 为溶剂， 反应 56.0h， 生成 6,7,8,9,10,11,12,13,14,16-decadeoxy-4,5-O-isopropylidene-D-glycero-L-threo-(E)-2-hexadecenono-1,15-lactone
  参考文献：
  名称：

  A general approach to enantiomerically pure methylcarbinols. Asymmetric synthesis of antibiotic (-)-A26771B and the WCR sex pheromone

  摘要：

  Either (R) or (S) enantiomerically pure methylcarbinol groups are conveniently produced from monosubstituted alkenes via the Sharpless asymmetric dihydroxylation (AD) reaction. The initial AD product, 1,2-dihydroxyalkane, obtained with predictable absolute configuration and high enantiomeric purity, is converted into 2-acetoxy-1-bromoalkane and then subjected to reductive debromination. These conditions are compatible with a variety of functional groups, including acetal, ester, nitrile, ketone, and silyl ether. The advantages of this method are demonstrated by highly efficient, asymmetric syntheses of enantiomerically pure natural products. All four stereoisomers of the WCR sex pheromone 4 are prepared in six steps form nona-1,8-diene in 10-15% overall yield. Similarly, a highly efficient formal total synthesis of antibiotic (-)-A26771B (5) is accomplished via two alternative approaches. The first one transforms dodec-11-enal into enantiomerically pure 5 in 11 steps and 4.1% overall yield, while the second achieves the same transformation in 12 steps and 6.6% overall yield.

  DOI：

  10.1021/jo00079a024
• 作为产物：
  描述：

  (2E,4E)-Hexadeca-2,4,15-trienoic acid methyl ester 在 AD-mix-α 、 甲基磺酰胺 、 对甲苯磺酸 作用下， 以 水 、 丙酮 、 叔丁醇 为溶剂， 反应 25.0h， 生成 Methyl (4S,5S,15S)-4,5,15,16-tetrahydroxyhexadec-2-enoate bis-acetonide
  参考文献：
  名称：

  A general approach to enantiomerically pure methylcarbinols. Asymmetric synthesis of antibiotic (-)-A26771B and the WCR sex pheromone

  摘要：

  Either (R) or (S) enantiomerically pure methylcarbinol groups are conveniently produced from monosubstituted alkenes via the Sharpless asymmetric dihydroxylation (AD) reaction. The initial AD product, 1,2-dihydroxyalkane, obtained with predictable absolute configuration and high enantiomeric purity, is converted into 2-acetoxy-1-bromoalkane and then subjected to reductive debromination. These conditions are compatible with a variety of functional groups, including acetal, ester, nitrile, ketone, and silyl ether. The advantages of this method are demonstrated by highly efficient, asymmetric syntheses of enantiomerically pure natural products. All four stereoisomers of the WCR sex pheromone 4 are prepared in six steps form nona-1,8-diene in 10-15% overall yield. Similarly, a highly efficient formal total synthesis of antibiotic (-)-A26771B (5) is accomplished via two alternative approaches. The first one transforms dodec-11-enal into enantiomerically pure 5 in 11 steps and 4.1% overall yield, while the second achieves the same transformation in 12 steps and 6.6% overall yield.

  DOI：

  10.1021/jo00079a024

文献信息

• A general approach to enantiomerically pure methylcarbinols. Asymmetric synthesis of antibiotic (-)-A26771B and the WCR sex pheromone
  作者：Subhash C. Sinha、Anjana Sinha-Bagchi、Ehud Keinan

  DOI：10.1021/jo00079a024

  日期：1993.12

  Either (R) or (S) enantiomerically pure methylcarbinol groups are conveniently produced from monosubstituted alkenes via the Sharpless asymmetric dihydroxylation (AD) reaction. The initial AD product, 1,2-dihydroxyalkane, obtained with predictable absolute configuration and high enantiomeric purity, is converted into 2-acetoxy-1-bromoalkane and then subjected to reductive debromination. These conditions are compatible with a variety of functional groups, including acetal, ester, nitrile, ketone, and silyl ether. The advantages of this method are demonstrated by highly efficient, asymmetric syntheses of enantiomerically pure natural products. All four stereoisomers of the WCR sex pheromone 4 are prepared in six steps form nona-1,8-diene in 10-15% overall yield. Similarly, a highly efficient formal total synthesis of antibiotic (-)-A26771B (5) is accomplished via two alternative approaches. The first one transforms dodec-11-enal into enantiomerically pure 5 in 11 steps and 4.1% overall yield, while the second achieves the same transformation in 12 steps and 6.6% overall yield.