Methyl 4,5-epoxy-2,3-O-isopropylidene-L-lyxonate | 114578-96-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 4,5-epoxy-2,3-O-isopropylidene-L-lyxonate
• 英文别名: methyl (4R,5R)-2,2-dimethyl-5-[(2S)-oxiran-2-yl]-1,3-dioxolane-4-carboxylate
• CAS: 114578-96-0
• 化学式: C₉H₁₄O₅
• 分子量: 202.207
• InChiKey: OCKSNXIKAWFJIR-RRKCRQDMSA-N

物化性质

• 沸点：
  238.6±40.0 °C(predicted)
• 密度：
  1.227±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  57.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 4,5-epoxy-2,3-O-isopropylidene-L-lyxonate 在 potassium acetate 、 硫脲 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 64.0h， 生成 5-O-Acetyl-2,3-O-isopropylidene-4-thio-D-ribono-1,4-lactone
  参考文献：
  名称：

  First synthesis of aldopentono-1,4-thiolactones

  摘要：

  A convenient synthesis of enantiomerically pure aldopentono-1,4-thiolactones is described. Thus, 4-thio-D-ribono-1,4-lactone (12) has been prepared from D-gluono-1,4-lactone (1), via its 2,3-O-isopropylidene derivative 3. The 5,6-glycol system of 3 was oxidized with NaIO4. Chemoselective reduction of the resulting aldehyde function with NaBH3CN led to 2,3-O-isopropylidene-L-lyxono-1,4-lactone (7). Tosylation of 7 and subsequent treatment of the tosylate 8 with sodium methoxide afforded methyl 4,5-epoxy-2,3-O-isopropylidene-L-lyxonate (9) as a key intermediate. Treatment of 9 with thiourea gave the 4,5-thiirane derivative having the D-ribo configuration (10). Regioselective opening of the thiirane ring and simultaneous thiolactonization took place by heating 10 with KOAc-HOAc-DMF. The resulting 5-O-acetyl-2,3-0-isopropylidene-4-thio-D-ribono-1,4-lactone (11) was readily converted, by acid removal (2 % HCI) of the protecting groups, into the crystalline thiolactone 12. A similar approach was employed for the synthesis of 4-thio-L-lyxono-1,4-lactone (19), starting from D-ribono-1,4-lactone (13).

  DOI：

  10.1021/jo00079a034
• 作为产物：
  描述：

  2,3-O-异亚丙基-D-核糖酸 gamma-内酯 在 sodium methylate 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 生成 Methyl 4,5-epoxy-2,3-O-isopropylidene-L-lyxonate
  参考文献：
  名称：

  Total synthesis of (+)-eldanolide from -ribonolactone

  摘要：

  DOI：

  10.1016/s0040-4039(00)84573-6

文献信息

• First synthesis of aldopentono-1,4-thiolactones
  作者：Oscar Varela、Patricia A. Zunszain

  DOI：10.1021/jo00079a034

  日期：1993.12

  A convenient synthesis of enantiomerically pure aldopentono-1,4-thiolactones is described. Thus, 4-thio-D-ribono-1,4-lactone (12) has been prepared from D-gluono-1,4-lactone (1), via its 2,3-O-isopropylidene derivative 3. The 5,6-glycol system of 3 was oxidized with NaIO4. Chemoselective reduction of the resulting aldehyde function with NaBH3CN led to 2,3-O-isopropylidene-L-lyxono-1,4-lactone (7). Tosylation of 7 and subsequent treatment of the tosylate 8 with sodium methoxide afforded methyl 4,5-epoxy-2,3-O-isopropylidene-L-lyxonate (9) as a key intermediate. Treatment of 9 with thiourea gave the 4,5-thiirane derivative having the D-ribo configuration (10). Regioselective opening of the thiirane ring and simultaneous thiolactonization took place by heating 10 with KOAc-HOAc-DMF. The resulting 5-O-acetyl-2,3-0-isopropylidene-4-thio-D-ribono-1,4-lactone (11) was readily converted, by acid removal (2 % HCI) of the protecting groups, into the crystalline thiolactone 12. A similar approach was employed for the synthesis of 4-thio-L-lyxono-1,4-lactone (19), starting from D-ribono-1,4-lactone (13).
• Total synthesis of (+)-eldanolide from -ribonolactone
  作者：R.M. Ortuño、R. Mercé、J. Font

  DOI：10.1016/s0040-4039(00)84573-6

  日期：1986.1