(1'R,2S)-2-<(Ethoxycarbonyl)amino>-3-methylbutanoic acid 1-vinylpent-4-enyl ester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1'R,2S)-2-<(Ethoxycarbonyl)amino>-3-methylbutanoic acid 1-vinylpent-4-enyl ester
• 英文别名: [(3R)-6-methylhepta-1,6-dien-3-yl] (2S)-2-(ethoxycarbonylamino)-3-methylbutanoate
• 化学式: C₁₆H₂₇NO₄
• 分子量: 297.395
• InChiKey: KKTNAMMODJDYEX-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  21
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  L-缬氨酸 在 4-二甲氨基吡啶 、 碳酸氢钠 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 (1'R,2S)-2-<(Ethoxycarbonyl)amino>-3-methylbutanoic acid 1-vinylpent-4-enyl ester
  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%.