ethyl (3S,4S)-isopropyl-4,5-O-isopropylidenepentanoate

• 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: ethyl (3S,4S)-isopropyl-4,5-O-isopropylidenepentanoate
• 英文别名: ethyl (3S)-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methylpentanoate
• 化学式: C₁₃H₂₄O₄
• 分子量: 244.331
• InChiKey: LTPGOHZNPPSJCS-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (3S,4S)-isopropyl-4,5-O-isopropylidenepentanoate 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 (4R,3S)-4,5-dihydroxy-3-(1-methylethyl)pentanoic acid γ-lactone
  参考文献：
  名称：

  Syn-Selective Michael Addition of Nitromethane Derivatives to Enoates Derived from (R)-(+)-Glyceraldehyde Acetonide

  摘要：

  We report the syn-selective Michael addition of a series of substituted primary and secondary nitromethane derivatives 4a-g to chiral enoates (Z)-2a and (E)-2a in the presence of TBAF . 3H(2)O or DBU. Regardless of the base employed, adducts syn-5a-g were obtained in good de (80-100%) from the reactions of 4a-g with (Z)-2a. However, in the addition to (E)-2a, the syn-diastereoselectivities depended on the structure of the nucleophile (80-90% de for nitromethane (4a), 80% de for phenylnitromethane (4g), 50 and 34% de for the primary nitromethane derivatives 4b and 4d, and 0 and 6% de for the secondary nitromethane derivatives 4e and 4f). A mixture of epimers (2:1/1:1) was obtained at the chiral center bearing the nitro group in 5b and 5d-g. The syn/anti ratio C-3,C-4 is kinetically controlled, while the epimeric ratio at the CNO2 chiral center (C-1') seems to be thermodynamically controlled. Adducts 5a,b,c,g were transformed into the respective cis-beta,gamma-disubstituted gamma-butyrolactones 6a, 7, 9a, and 9e. A mechanistic rationale to explain the observed diastereoselectivities is proposed.

  DOI：

  10.1021/jo960788x
• 作为产物：
  描述：

  ethyl (Z)-3-((S)-2,2-dimethyl-1,3-dioxolan-4-yl)acrylate 在 偶氮二异丁腈 、 四丁基氟化铵 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 4.5h， 生成 ethyl (3S,4S)-isopropyl-4,5-O-isopropylidenepentanoate
  参考文献：
  名称：

  Syn-Selective Michael Addition of Nitromethane Derivatives to Enoates Derived from (R)-(+)-Glyceraldehyde Acetonide

  摘要：

  We report the syn-selective Michael addition of a series of substituted primary and secondary nitromethane derivatives 4a-g to chiral enoates (Z)-2a and (E)-2a in the presence of TBAF . 3H(2)O or DBU. Regardless of the base employed, adducts syn-5a-g were obtained in good de (80-100%) from the reactions of 4a-g with (Z)-2a. However, in the addition to (E)-2a, the syn-diastereoselectivities depended on the structure of the nucleophile (80-90% de for nitromethane (4a), 80% de for phenylnitromethane (4g), 50 and 34% de for the primary nitromethane derivatives 4b and 4d, and 0 and 6% de for the secondary nitromethane derivatives 4e and 4f). A mixture of epimers (2:1/1:1) was obtained at the chiral center bearing the nitro group in 5b and 5d-g. The syn/anti ratio C-3,C-4 is kinetically controlled, while the epimeric ratio at the CNO2 chiral center (C-1') seems to be thermodynamically controlled. Adducts 5a,b,c,g were transformed into the respective cis-beta,gamma-disubstituted gamma-butyrolactones 6a, 7, 9a, and 9e. A mechanistic rationale to explain the observed diastereoselectivities is proposed.

  DOI：

  10.1021/jo960788x

文献信息

• Syn-Selective Michael Addition of Nitromethane Derivatives to Enoates Derived from (<i>R</i>)-(+)-Glyceraldehyde Acetonide
  作者：Jeronimo S. Costa、Ayres G. Dias、Aline L. Anholeto、Mônica D. Monteiro、Vera L. Patrocinio、Paulo R. R. Costa

  DOI：10.1021/jo960788x

  日期：1997.6.13

  We report the syn-selective Michael addition of a series of substituted primary and secondary nitromethane derivatives 4a-g to chiral enoates (Z)-2a and (E)-2a in the presence of TBAF . 3H(2)O or DBU. Regardless of the base employed, adducts syn-5a-g were obtained in good de (80-100%) from the reactions of 4a-g with (Z)-2a. However, in the addition to (E)-2a, the syn-diastereoselectivities depended on the structure of the nucleophile (80-90% de for nitromethane (4a), 80% de for phenylnitromethane (4g), 50 and 34% de for the primary nitromethane derivatives 4b and 4d, and 0 and 6% de for the secondary nitromethane derivatives 4e and 4f). A mixture of epimers (2:1/1:1) was obtained at the chiral center bearing the nitro group in 5b and 5d-g. The syn/anti ratio C-3,C-4 is kinetically controlled, while the epimeric ratio at the CNO2 chiral center (C-1') seems to be thermodynamically controlled. Adducts 5a,b,c,g were transformed into the respective cis-beta,gamma-disubstituted gamma-butyrolactones 6a, 7, 9a, and 9e. A mechanistic rationale to explain the observed diastereoselectivities is proposed.