Methyl 4,5-dideoxy-4,5-epithio-2,3-O-isopropylidene-D-ribonate | 151930-66-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 4,5-dideoxy-4,5-epithio-2,3-O-isopropylidene-D-ribonate
• 英文别名: methyl (4R,5S)-2,2-dimethyl-5-[(2S)-thiiran-2-yl]-1,3-dioxolane-4-carboxylate
• CAS: 151930-66-4
• 化学式: C₉H₁₄O₄S
• 分子量: 218.274
• InChiKey: ULNANWTWPPHAEZ-FSDSQADBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 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：
  70.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl 4,5-dideoxy-4,5-epithio-2,3-O-isopropylidene-D-ribonate 在 盐酸 、 potassium acetate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.0h， 生成 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-Isopropylidene-5-O-(p-tolylsulfonyl)-L-lyxono-1,4-lactone 在 sodium methylate 、 硫脲 作用下， 以 甲醇 为溶剂， 反应 48.33h， 生成 Methyl 4,5-dideoxy-4,5-epithio-2,3-O-isopropylidene-D-ribonate
  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

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).