tolyl 2,3-anhydro-1-thio-α-D-[1-D]-lyxofuranoside | 1187662-91-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: tolyl 2,3-anhydro-1-thio-α-D-[1-D]-lyxofuranoside
• CAS: 1187662-91-4
• 化学式: C₁₂H₁₄O₃S
• 分子量: 239.299
• InChiKey: WUQPBDOOBLGRBX-USCFUXMMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  41.99
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tolyl 2,3-anhydro-1-thio-α-D-[1-D]-lyxofuranoside 、 溶剂黄146 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 以80%的产率得到tolyl 2,3-anhydro-5-O-acetyl-1-thio-α-D-(50percent-1-D)-lyxofuranoside
  参考文献：
  名称：

  2,3-Anhydrosugars in Glycoside Bond Synthesis: Mechanism of 2-Deoxy-2-thioaryl Glycoside Formation

  摘要：

  A series of investigations probing the mechanism of the 2,3-anhydrosugar migration-glycosylation reaction were performed using a thioglycoside with the D-lyxo stereochemistry as the substrate. Among the work reported are the results of quantum mechanical calculations, NMR studies, the measurement of a-deuterium kinetic isotope effects, and the synthesis of a series of substrate analogues. All studies point to a consistent finding: that the reaction proceeds through an oxocarbenium ion intermediate, not an episulfonium ion as previously suggested. It is proposed that the high stereoselectivity of the reaction arises from a preferred "inside attack" of the nucleophile onto the oxocarbenium ion intermediate.

  DOI：

  10.1021/ja9029945
• 作为产物：
  描述：

  tolyl 2,3-anhydro-5-O-benzoyl-1-thio-α-D-[1-D]-lyxofuranoside 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 以83%的产率得到tolyl 2,3-anhydro-1-thio-α-D-[1-D]-lyxofuranoside
  参考文献：
  名称：

  2,3-Anhydrosugars in Glycoside Bond Synthesis: Mechanism of 2-Deoxy-2-thioaryl Glycoside Formation

  摘要：

  A series of investigations probing the mechanism of the 2,3-anhydrosugar migration-glycosylation reaction were performed using a thioglycoside with the D-lyxo stereochemistry as the substrate. Among the work reported are the results of quantum mechanical calculations, NMR studies, the measurement of a-deuterium kinetic isotope effects, and the synthesis of a series of substrate analogues. All studies point to a consistent finding: that the reaction proceeds through an oxocarbenium ion intermediate, not an episulfonium ion as previously suggested. It is proposed that the high stereoselectivity of the reaction arises from a preferred "inside attack" of the nucleophile onto the oxocarbenium ion intermediate.

  DOI：

  10.1021/ja9029945