(E)-3-oxo-retro-α-ionol | 102488-07-3

• 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: (E)-3-oxo-retro-α-ionol
• 英文别名: Jhwwvzzgblpjpw-sdqbbnpisa-；(4E)-4-(3-hydroxybutylidene)-3,5,5-trimethylcyclohex-2-en-1-one
• CAS: 102488-07-3
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: JHWWVZZGBLPJPW-SDQBBNPISA-N

物化性质

• 沸点：
  332.8±21.0 °C(Predicted)
• 密度：
  1.037±0.06 g/cm3(Predicted)
• 保留指数：
  2756

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-3-oxo-retro-α-ionol 生成 (6E,9S)-9-hydroxy-4,6-megastigmadien-3-one
  参考文献：
  名称：

  Synthesis and Enantiodifferentiation of Isomeric 2,3,5,6,8,8a-Hexahydro-2,5,5,8a-tetramethyl-7H-1-benzopyran-7-ones (3,4-Dihydro-3-oxoedulans)

  摘要：

  The benzopyran derivatives 1a-d mere prepared in a biomimetic type reaction from their presumed natural precursor 3-oxo-retro-alpha-ionol, which was available from alpha-ionone by tert-butyl chromate oxidation, reduction with NaBH4, and subsequent rearrangement of the 7,8 double bond. The so-obtained geometrical isomers of 3-oxo-retro-alpha-ionol (4a/b) were separated by preparative and analytical multilayer coil countercurrent chromatography. Racemic 3-oxo-retro-alpha-ionol (4a) was esterified with (R)-(-)-2-phenylpropionic acid, and the resulting diastereomeric esters (5a/b) were isolated in pure form by preparative HPLC. Configuration at C-9 was determined by H-1 NMR spectroscopy. The isomeric ketols 6a/b obtained from esters 5a/b by enzymatic hydrolysis were subjected to thermal treatment (simultaneous distillation extraction, pH 1), yielding two pairs of diastereomeric 3,4-dihydro-3-oxoedulans (1a/b and 1c/d). The absolute configuration at C-8a was established by NOE experiments. Using on-line coupled multidimensional gas chromatography-mass spectrometry [DB-Wax/octakis(2,6-di-O-methyl-3-O-pentyl)-gamma-cyclodextrin] with selected ion monitoring mode, enantiodifferentiation of 1a-d in a number of natural sources was carried out.

  DOI：

  10.1021/jf00055a026
• 作为产物：
  描述：

  3-oxo-α-ionol 在 sodium methylate 作用下， 生成 (Z)-4-(3-hydroxybutylidene)-3,5,5-trimethyl-2-cyclohexen-1-one 、 (E)-3-oxo-retro-α-ionol
  参考文献：
  名称：

  Synthesis and Enantiodifferentiation of Isomeric 3,5,6,8a-Tetrahydro-2,5,5,8a-tetramethyl-2H-1-benzopyrans (Edulans I and II)

  摘要：

  The benzopyran derivatives 1a-d were prepared in a biomimetic-type reaction from their natural precursor 3-hydroxy-retro-alpha-ionol (6) which was available from alpha-ionol by tert-butyl chromate oxidation, reduction with NaBH4, and subsequent rearrangement of the 7,8 double bond. The so-obtained geometrical isomers 8-oxo-retro-alpha-ionol 4a/b were separated by preparative and analytical multilayer coil countercurrent chromatography. The racemic 3-oxo-retro-alpha-ionol 4a was esterified with (R)-(-)-2-phenylpropionic acid, and the resulting diastereomeric esters (5a/b) were isolated in pure form (de 90%) by preparative HPLC. Configuration at C-9 was determined by H-1 NMR spectroscopy. The isomeric diols 6a/b obtained from esters 5a/b by LiAlH4 reductive cleavage were subjected to thermal treatment (simultaneous distillation extraction), yielding two pairs of diastereomeric edulans (1a/b and 1c/d) which were subsequently obtained in optically pure form by analytical HPLC. The absolute configuration at C-8a was established by NOE experiments. Using on-line coupled multidimensional gas chromatography-mass spectrometry [DB-Wax/heptakis-(2,6-di-O-methyl-3-O-pentyl)-beta- cyclodextrin] with selected ion monitoring mode, enantiodifferentiation of 1a-d in a number of natural sources revealed predominance of the 2S enantiomers.

  DOI：

  10.1021/jf00049a034

文献信息

• Ito, Nobuhiko; Etoh, Takeaki; Hagiwara, Hisahiro, Journal of the Chemical Society. Perkin transactions I, 1997, # 10, p. 1571 - 1579
  作者：Ito, Nobuhiko、Etoh, Takeaki、Hagiwara, Hisahiro、Kato, Michiharu

  DOI：——

  日期：——
• SEFTON, MARK A.;SKOUROUMOUNIS, GEORGE K.;MASSY-WESTROPP, RALPH A.;WILLIAM+, AUSTRAL. J. CHEM., 42,(1989) N2, C. 2071-2084
  作者：SEFTON, MARK A.、SKOUROUMOUNIS, GEORGE K.、MASSY-WESTROPP, RALPH A.、WILLIAM+

  DOI：——

  日期：——
• Synthesis and Enantiodifferentiation of Isomeric 3,5,6,8a-Tetrahydro-2,5,5,8a-tetramethyl-2H-1-benzopyrans (Edulans I and II)
  作者：Gertraut Schmidt、Gerhard Full、Peter Winterhalter、Peter Schreier

  DOI：10.1021/jf00049a034

  日期：1995.1

  The benzopyran derivatives 1a-d were prepared in a biomimetic-type reaction from their natural precursor 3-hydroxy-retro-alpha-ionol (6) which was available from alpha-ionol by tert-butyl chromate oxidation, reduction with NaBH4, and subsequent rearrangement of the 7,8 double bond. The so-obtained geometrical isomers 8-oxo-retro-alpha-ionol 4a/b were separated by preparative and analytical multilayer coil countercurrent chromatography. The racemic 3-oxo-retro-alpha-ionol 4a was esterified with (R)-(-)-2-phenylpropionic acid, and the resulting diastereomeric esters (5a/b) were isolated in pure form (de 90%) by preparative HPLC. Configuration at C-9 was determined by H-1 NMR spectroscopy. The isomeric diols 6a/b obtained from esters 5a/b by LiAlH4 reductive cleavage were subjected to thermal treatment (simultaneous distillation extraction), yielding two pairs of diastereomeric edulans (1a/b and 1c/d) which were subsequently obtained in optically pure form by analytical HPLC. The absolute configuration at C-8a was established by NOE experiments. Using on-line coupled multidimensional gas chromatography-mass spectrometry [DB-Wax/heptakis-(2,6-di-O-methyl-3-O-pentyl)-beta- cyclodextrin] with selected ion monitoring mode, enantiodifferentiation of 1a-d in a number of natural sources revealed predominance of the 2S enantiomers.
• Synthesis and Enantiodifferentiation of Isomeric 2,3,5,6,8,8a-Hexahydro-2,5,5,8a-tetramethyl-7H-1-benzopyran-7-ones (3,4-Dihydro-3-oxoedulans)
  作者：Gertraut Schmidt、Wolfgang Neugebauer、Peter Winterhalter、Peter Schreier

  DOI：10.1021/jf00055a026

  日期：1995.7

  The benzopyran derivatives 1a-d mere prepared in a biomimetic type reaction from their presumed natural precursor 3-oxo-retro-alpha-ionol, which was available from alpha-ionone by tert-butyl chromate oxidation, reduction with NaBH4, and subsequent rearrangement of the 7,8 double bond. The so-obtained geometrical isomers of 3-oxo-retro-alpha-ionol (4a/b) were separated by preparative and analytical multilayer coil countercurrent chromatography. Racemic 3-oxo-retro-alpha-ionol (4a) was esterified with (R)-(-)-2-phenylpropionic acid, and the resulting diastereomeric esters (5a/b) were isolated in pure form by preparative HPLC. Configuration at C-9 was determined by H-1 NMR spectroscopy. The isomeric ketols 6a/b obtained from esters 5a/b by enzymatic hydrolysis were subjected to thermal treatment (simultaneous distillation extraction, pH 1), yielding two pairs of diastereomeric 3,4-dihydro-3-oxoedulans (1a/b and 1c/d). The absolute configuration at C-8a was established by NOE experiments. Using on-line coupled multidimensional gas chromatography-mass spectrometry [DB-Wax/octakis(2,6-di-O-methyl-3-O-pentyl)-gamma-cyclodextrin] with selected ion monitoring mode, enantiodifferentiation of 1a-d in a number of natural sources was carried out.

表征谱图