(1'S,2S)-2-Hydroxysuccinic acid 4-(4'-methyl-1'-vinylpent-4'-enyl) ester dimethyl ketal

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1'S,2S)-2-Hydroxysuccinic acid 4-(4'-methyl-1'-vinylpent-4'-enyl) ester dimethyl ketal
• 英文别名: [(3S)-6-methylhepta-1,6-dien-3-yl] 2-[(4S)-2,2-dimethyl-5-oxo-1,3-dioxolan-4-yl]acetate
• 化学式: C₁₅H₂₂O₅
• 分子量: 282.337
• InChiKey: BNCBTBWTNRTQSB-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (S)-[2,2-二甲基-5-氧代二氧戊环-4-基]乙酸 、 6-methyl-1,6-heptadien-3-ol 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 生成 (1'S,2S)-2-Hydroxysuccinic acid 4-(4'-methyl-1'-vinylpent-4'-enyl) ester dimethyl ketal 、 (1'R,2S)-2-Hydroxysuccinic acid 4-(4'-methyl-1'-vinylpent-4'-enyl) ester dimethyl ketal
  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%.