(S)-6-Methyl-1,6-heptadien-3-ol | 169868-22-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-6-Methyl-1,6-heptadien-3-ol
• 英文别名: (3S)-6-methylhepta-1,6-dien-3-ol
• CAS: 169868-22-8
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: INSRWNOFDDRAKZ-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-6-Methyl-1,6-heptadien-3-ol 在 chromium(VI) oxide 、 硫酸 、 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 1.0h， 生成 (+/-)5-methylbicyclo<3.2.0>heptan-2-one
  参考文献：
  名称：

  Stereoselective Intramolecular Copper(I)-Catalyzed [2 + 2]- Photocycloadditions. Enantioselective Synthesis of (+)- and (-)-Grandisol

  摘要：

  This work deals with copper(I)-catalyzed intramolecular [2 + 2]-photocycloadditions of 1,6-diene derivatives. The bridgehead carbons C-l and C-5 of the resulting bicyclo[3.2.0]heptanes are generated stereoselectively by using chiral starting material, chiral catalysts, or chiral auxiliaries. The irradiation of (S)-3 leads to enantiomerically pure 4 and 5 which opens a new synthetic route to enantiomerically pure (+)- and (-)-grandisol 9. The use of chiral copper complexes as catalysts delivers enantiomeric excesses below 5%. The reason for these small excesses is a low reactivity of the chiral copper complexes, as confirmed by CD-spectroscopic measurements. Malic acid or amino carboxylic acid derivatives as chiral auxiliaries yield the bicyclic alcohols 4 and 5 with enantiomeric excesses up to 15%. The employment of a chiral diol as an auxiliary delivers a chiral ketal 36, and the resulting ketone 7 exhibits enantiomeric excesses up to 60%.

  DOI：

  10.1021/jo00127a034
• 作为产物：
  描述：

  4-溴-2-甲基-1-丁烯 、 丙烯醛 生成 (S)-6-Methyl-1,6-heptadien-3-ol
  参考文献：
  名称：

  Stereoselective Intramolecular Copper(I)-Catalyzed [2 + 2]- Photocycloadditions. Enantioselective Synthesis of (+)- and (-)-Grandisol

  摘要：

  This work deals with copper(I)-catalyzed intramolecular [2 + 2]-photocycloadditions of 1,6-diene derivatives. The bridgehead carbons C-l and C-5 of the resulting bicyclo[3.2.0]heptanes are generated stereoselectively by using chiral starting material, chiral catalysts, or chiral auxiliaries. The irradiation of (S)-3 leads to enantiomerically pure 4 and 5 which opens a new synthetic route to enantiomerically pure (+)- and (-)-grandisol 9. The use of chiral copper complexes as catalysts delivers enantiomeric excesses below 5%. The reason for these small excesses is a low reactivity of the chiral copper complexes, as confirmed by CD-spectroscopic measurements. Malic acid or amino carboxylic acid derivatives as chiral auxiliaries yield the bicyclic alcohols 4 and 5 with enantiomeric excesses up to 15%. The employment of a chiral diol as an auxiliary delivers a chiral ketal 36, and the resulting ketone 7 exhibits enantiomeric excesses up to 60%.

  DOI：

  10.1021/jo00127a034

文献信息

• Stereoselective Intramolecular Copper(I)-Catalyzed [2 + 2]- Photocycloadditions. Enantioselective Synthesis of (+)- and (-)-Grandisol
  作者：Klaus Langer、Jochen Mattay

  DOI：10.1021/jo00127a034

  日期：1995.11

  This work deals with copper(I)-catalyzed intramolecular [2 + 2]-photocycloadditions of 1,6-diene derivatives. The bridgehead carbons C-l and C-5 of the resulting bicyclo[3.2.0]heptanes are generated stereoselectively by using chiral starting material, chiral catalysts, or chiral auxiliaries. The irradiation of (S)-3 leads to enantiomerically pure 4 and 5 which opens a new synthetic route to enantiomerically pure (+)- and (-)-grandisol 9. The use of chiral copper complexes as catalysts delivers enantiomeric excesses below 5%. The reason for these small excesses is a low reactivity of the chiral copper complexes, as confirmed by CD-spectroscopic measurements. Malic acid or amino carboxylic acid derivatives as chiral auxiliaries yield the bicyclic alcohols 4 and 5 with enantiomeric excesses up to 15%. The employment of a chiral diol as an auxiliary delivers a chiral ketal 36, and the resulting ketone 7 exhibits enantiomeric excesses up to 60%.