5-O-Acetyl-2,3-O-isopropylidene-4-thio-L-lyxono-1,4-lactone | 151930-70-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-O-Acetyl-2,3-O-isopropylidene-4-thio-L-lyxono-1,4-lactone
• 英文别名: [(3aR,6S,6aS)-2,2-dimethyl-4-oxo-6,6a-dihydro-3aH-thieno[3,4-d][1,3]dioxol-6-yl]methyl acetate
• CAS: 151930-70-0
• 化学式: C₁₀H₁₄O₅S
• 分子量: 246.284
• InChiKey: CBZPHPQCWDFKFW-XLPZGREQSA-N

物化性质

• 沸点：
  359.1±42.0 °C(Predicted)
• 密度：
  1.250±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  87.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-O-Acetyl-2,3-O-isopropylidene-4-thio-L-lyxono-1,4-lactone 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以86%的产率得到4-thio-L-lyxono-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：

  methyl (4R,5R)-2,2-dimethyl-5-(oxiran-2-yl)-1,3-dioxolane-4-carboxylate 在 potassium acetate 、 硫脲 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 66.0h， 生成 5-O-Acetyl-2,3-O-isopropylidene-4-thio-L-lyxono-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