ethyl (2S,3S,4S)-2-methyl-3-nitromethyl-4,5-isopropylidenedioxypentanoate | 467425-71-4

• 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 (2S,3S,4S)-2-methyl-3-nitromethyl-4,5-isopropylidenedioxypentanoate
• 英文别名: ethyl (2S,3S)-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-methyl-4-nitrobutanoate
• CAS: 467425-71-4
• 化学式: C₁₂H₂₁NO₆
• 分子量: 275.302
• InChiKey: SQVBEGZZDCCYOH-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 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：
  90.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl (2S,3S,4S)-2-methyl-3-nitromethyl-4,5-isopropylidenedioxypentanoate 在 盐酸 作用下， 以 甲醇 、 水 为溶剂， 反应 2.0h， 以100%的产率得到(3S,4S,5S)-5-hydroxymethyl-3-methyl-4-nitromethyldihydrofuran-2-one
  参考文献：
  名称：

  Selective conjugate addition of nitromethane to enoates derived from d-mannitol and l-tartaric acid

  摘要：

  The conjugate addition of nitromethane to enoates prepared from D-(+)-mannitol, substituted at the alpha-position by a methyl or a benzyl group, was investigated. While excellent syn-selectivity (d.e. >90%) was obtained from a-benzyl enoates (used as a mixture of epimers, E/Z=1.8:1), for alpha-methyl enoates the selectivity depended on the stereochemistry of the double bond in the acceptor (d.e. >90% for the (Z)-enoate and 50% for the (E)-enoate). In all cases, a mixture of epimers was formed at the newly generated stereocenter at the a-position. The epimeric syn-adducts were transformed into the corresponding pure alpha,beta,gamma-trisubstituted gamma-butyrolactones by cyclization in acid medium followed by epimerization of the stereocenter at the a-position in DBU/CH2Cl2. When enoates derived from L-tartaric acid were used as acceptors, syn-selective conjugate additions were also observed (d.e. >90% for the (Z)-isomer and 50% for the (E)-isomer). The configuration at the newly generated stereogenic centers were assigned based on X-ray analyses, H-1-H-1 coupling constants and NOE experiments in NMR spectroscopy. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00230-6
• 作为产物：
  描述：

  三乙基2-膦酰基丙酯 在 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 7.5h， 生成 ethyl (2S,3S,4S)-2-methyl-3-nitromethyl-4,5-isopropylidenedioxypentanoate
  参考文献：
  名称：

  Selective conjugate addition of nitromethane to enoates derived from d-mannitol and l-tartaric acid

  摘要：

  The conjugate addition of nitromethane to enoates prepared from D-(+)-mannitol, substituted at the alpha-position by a methyl or a benzyl group, was investigated. While excellent syn-selectivity (d.e. >90%) was obtained from a-benzyl enoates (used as a mixture of epimers, E/Z=1.8:1), for alpha-methyl enoates the selectivity depended on the stereochemistry of the double bond in the acceptor (d.e. >90% for the (Z)-enoate and 50% for the (E)-enoate). In all cases, a mixture of epimers was formed at the newly generated stereocenter at the a-position. The epimeric syn-adducts were transformed into the corresponding pure alpha,beta,gamma-trisubstituted gamma-butyrolactones by cyclization in acid medium followed by epimerization of the stereocenter at the a-position in DBU/CH2Cl2. When enoates derived from L-tartaric acid were used as acceptors, syn-selective conjugate additions were also observed (d.e. >90% for the (Z)-isomer and 50% for the (E)-isomer). The configuration at the newly generated stereogenic centers were assigned based on X-ray analyses, H-1-H-1 coupling constants and NOE experiments in NMR spectroscopy. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00230-6

文献信息

• Selective conjugate addition of nitromethane to enoates derived from d-mannitol and l-tartaric acid
  作者：Américo C. Pinto、Cleide B.L. Freitas、Ayres G. Dias、Vera L.P. Pereira、Bernard Tinant、Jean-Paul Declercq、Paulo R.R. Costa

  DOI：10.1016/s0957-4166(02)00230-6

  日期：2002.6

  The conjugate addition of nitromethane to enoates prepared from D-(+)-mannitol, substituted at the alpha-position by a methyl or a benzyl group, was investigated. While excellent syn-selectivity (d.e. >90%) was obtained from a-benzyl enoates (used as a mixture of epimers, E/Z=1.8:1), for alpha-methyl enoates the selectivity depended on the stereochemistry of the double bond in the acceptor (d.e. >90% for the (Z)-enoate and 50% for the (E)-enoate). In all cases, a mixture of epimers was formed at the newly generated stereocenter at the a-position. The epimeric syn-adducts were transformed into the corresponding pure alpha,beta,gamma-trisubstituted gamma-butyrolactones by cyclization in acid medium followed by epimerization of the stereocenter at the a-position in DBU/CH2Cl2. When enoates derived from L-tartaric acid were used as acceptors, syn-selective conjugate additions were also observed (d.e. >90% for the (Z)-isomer and 50% for the (E)-isomer). The configuration at the newly generated stereogenic centers were assigned based on X-ray analyses, H-1-H-1 coupling constants and NOE experiments in NMR spectroscopy. (C) 2002 Elsevier Science Ltd. All rights reserved.