Phenyl 3,5-di-O-isopropylidene-2-deoxy-1-thio-α-L-threo-pentofuranoside | 163070-49-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Phenyl 3,5-di-O-isopropylidene-2-deoxy-1-thio-α-L-threo-pentofuranoside
• 英文别名: (4aS,6S,7aS)-2,2-dimethyl-6-phenylsulfanyl-4a,6,7,7a-tetrahydro-4H-furo[3,2-d][1,3]dioxine
• CAS: 163070-49-3
• 化学式: C₁₄H₁₈O₃S
• 分子量: 266.361
• InChiKey: IOLOCYFXPKFSEW-AVGNSLFASA-N

物化性质

• 沸点：
  375.9±42.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  53
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Phenyl 3,5-di-O-isopropylidene-2-deoxy-1-thio-α-L-threo-pentofuranoside 在 N-溴代丁二酰亚胺(NBS) 、 4 A molecular sieve 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.33h， 生成 β-L-2'-deoxy-xylo-thimidine
  参考文献：
  名称：

  Stereoselective Synthesis of 2'-Deoxy-.beta.-D-threo-pentofuranosyl Nucleosides by the NBS-Promoted Coupling Reaction of Thioglycosides with Silylated Heterocyclic Bases

  摘要：

  The NBS-promoted coupling reaction of phenyl 3,5-O-isopropylidene-2-deoxy-1-thio-alpha-D-threo-pentofuranoside (5e) with silylated pyrimidine bases was found to proceed in a highly stereoselective manner (alpha:beta = 1:24-0:1) to afford 2'-deoxy-beta-D-threo-pentofuranosyl pyrimidine nucleosides in satisfactory yields. The highly stereoselective outcome is thought to result from an in situ anomerization-type mechanism, in which intimate ionic intermediates would be in equilibrium and anomerize to the sterically preferable a form. A subsequent S(N)2 type attack to the intermediate will lead to the beta-nucleosides. By using this method, the synthesis of L-nucleosides, 1-(2-deoxy-beta-L-threo-pentofuranosyl)thymine and cytosine derivatives, was also demonstrated by starting from the L-enantiomer of the thioglycoside. On the other hand, the reaction with purine bases was accompanied by the production of undesirable N-7 regioisomers besides the desired N-9 products. The product distribution of the regioisomers was, however, proved to change with reaction time. For instance, a long reaction period allowed the thermodynamically stable N-9 isomers to be exclusively produced with moderate selectivity (alpha:beta = 1:2-1:4.8). The isolated yields of the 9-beta isomers after purification were acceptable for practical use.

  DOI：

  10.1021/jo00104a020
• 作为产物：
  描述：

  苯基乙烯基硫醚 在 三氟化硼乙醚 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 2.5h， 生成 Phenyl 3,5-di-O-isopropylidene-2-deoxy-1-thio-α-L-threo-pentofuranoside
  参考文献：
  名称：

  Stereoselective Synthesis of 2'-Deoxy-.beta.-D-threo-pentofuranosyl Nucleosides by the NBS-Promoted Coupling Reaction of Thioglycosides with Silylated Heterocyclic Bases

  摘要：

  The NBS-promoted coupling reaction of phenyl 3,5-O-isopropylidene-2-deoxy-1-thio-alpha-D-threo-pentofuranoside (5e) with silylated pyrimidine bases was found to proceed in a highly stereoselective manner (alpha:beta = 1:24-0:1) to afford 2'-deoxy-beta-D-threo-pentofuranosyl pyrimidine nucleosides in satisfactory yields. The highly stereoselective outcome is thought to result from an in situ anomerization-type mechanism, in which intimate ionic intermediates would be in equilibrium and anomerize to the sterically preferable a form. A subsequent S(N)2 type attack to the intermediate will lead to the beta-nucleosides. By using this method, the synthesis of L-nucleosides, 1-(2-deoxy-beta-L-threo-pentofuranosyl)thymine and cytosine derivatives, was also demonstrated by starting from the L-enantiomer of the thioglycoside. On the other hand, the reaction with purine bases was accompanied by the production of undesirable N-7 regioisomers besides the desired N-9 products. The product distribution of the regioisomers was, however, proved to change with reaction time. For instance, a long reaction period allowed the thermodynamically stable N-9 isomers to be exclusively produced with moderate selectivity (alpha:beta = 1:2-1:4.8). The isolated yields of the 9-beta isomers after purification were acceptable for practical use.

  DOI：

  10.1021/jo00104a020

文献信息

• Stereoselective Synthesis of 2'-Deoxy-.beta.-D-threo-pentofuranosyl Nucleosides by the NBS-Promoted Coupling Reaction of Thioglycosides with Silylated Heterocyclic Bases
  作者：Hideyuki Sugimura、Kenji Osumi、Yasuko Kodaka、Keiko Sujino

  DOI：10.1021/jo00104a020

  日期：1994.12

  The NBS-promoted coupling reaction of phenyl 3,5-O-isopropylidene-2-deoxy-1-thio-alpha-D-threo-pentofuranoside (5e) with silylated pyrimidine bases was found to proceed in a highly stereoselective manner (alpha:beta = 1:24-0:1) to afford 2'-deoxy-beta-D-threo-pentofuranosyl pyrimidine nucleosides in satisfactory yields. The highly stereoselective outcome is thought to result from an in situ anomerization-type mechanism, in which intimate ionic intermediates would be in equilibrium and anomerize to the sterically preferable a form. A subsequent S(N)2 type attack to the intermediate will lead to the beta-nucleosides. By using this method, the synthesis of L-nucleosides, 1-(2-deoxy-beta-L-threo-pentofuranosyl)thymine and cytosine derivatives, was also demonstrated by starting from the L-enantiomer of the thioglycoside. On the other hand, the reaction with purine bases was accompanied by the production of undesirable N-7 regioisomers besides the desired N-9 products. The product distribution of the regioisomers was, however, proved to change with reaction time. For instance, a long reaction period allowed the thermodynamically stable N-9 isomers to be exclusively produced with moderate selectivity (alpha:beta = 1:2-1:4.8). The isolated yields of the 9-beta isomers after purification were acceptable for practical use.