2,3:5,6-Di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose | 160701-79-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3:5,6-Di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose
• 英文别名: (3aS,4R,6R,6aS)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-4-(1,3-thiazol-2-yl)-6,6a-dihydro-3aH-furo[3,4-d][1,3]dioxol-4-ol
• CAS: 160701-79-1
• 化学式: C₁₅H₂₁NO₆S
• 分子量: 343.401
• InChiKey: YQKCGLVHKWGGLF-QMUJVDTISA-N

物化性质

• 沸点：
  468.546±45.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.322±0.06 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,3:5,6-Di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose 在 4 A molecular sieve 作用下， 以 甲苯 为溶剂， 反应 14.0h， 生成 2,3:5,6-二-O-异亚丙基-D-甘露糖酸-1,4-内酯
  参考文献：
  名称：

  Thiazole as Leaving Group. Thermal Elimination from Thiazolylketoses

  摘要：

  Heating thiazolylketofuranoses and -ketopyranoses in refluxing toluene results in the elimination of thiazole and formation of the corresponding sugar lactones in nearly quantitative yield. The same reaction does not occur with 1-O-acetyl and 1-O-trimethylsilyl derivatives. Also model furyl- and thienylketofuranoses and various thiazolyl alcohols proved to be stable under the above thermolysis conditions. A possible mechanism of the observed thermolysis of thiazolylketoses involves the thiazolium 2-ylide as the actual leaving group.

  DOI：

  10.3987/com-98-8154
• 作为产物：
  描述：

  2,3,5,6-di-O-isopropylidene-D-mannofuranose 在 正丁基锂 、 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.17h， 生成 2,3:5,6-Di-O-isopropylidene-1-(2-thiazolyl)-α-D-mannofuranose
  参考文献：
  名称：

  Thiazole-Based Synthesis of Formyl C-Glycosides

  摘要：

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.

  DOI：

  10.1021/jo00100a050

文献信息

• Selectivity in the SmI2-induced deoxygenation of thiazolylketoses for formyl C-glycoside synthesis and revised structure of C-ribofuranosides
  作者：Alessandro Dondoni、Paolo Formaglio、Alberto Marra、Alessandro Massi

  DOI：10.1016/s0040-4020(01)00736-0

  日期：2001.9

  Deoxygenation of thiazolylketose acetates using SmI2–(CH2OH)2 or TMSOTf–Et3SiH affords thiazolyl C-glycosides with opposite α/β ratios. Examination of the thiazolyl α- and β-C-ribofuranoside pair by NOE experiments reveals that the earlier configuration assigned to one of these isomers has to be revised. Having prepared authentic anomeric α- and β-ribofuranose aldehydes from the corresponding thiazolyl

  使用SmI 2-（CH 2 OH）2或TMSOTf-Et 3 SiH对乙酸噻唑基酮糖乙酸进行脱氧，得到具有相反α/β比的噻唑基C-糖苷。通过NOE实验对噻唑基α-和β- C-核呋喃糖苷对的研究表明，必须修改分配给这些异构体之一的早期构型。已经制备正品异头α-和β-D-呋喃核糖醛从相应的噻唑基C ^由噻唑环的裂解-glycosides，各醛转化到（1→6） - c ^通过Wittig烯化-disaccharides与半乳糖6-正膦。
• Thiazole-Based Synthesis of Formyl C-Glycosides
  作者：Alessandro Dondoni、Marie-Christine Scherrmann

  DOI：10.1021/jo00100a050

  日期：1994.10

  A method for the installation of the formyl group at the anomeric position of pyranoses and furanoses starting from the corresponding lactones has been developed. The strategy involves the addition of 2-lithiothiazole to the sugar lactone, followed by the silane reduction of the acetylated resultant ketol and the unmasking of the formyl group from the thiazole ring. All steps have been studied in some details to improve chemical efficiency and stereochemical control. Hence, reversed alpha:beta ratios of ketols were found in kinetic and thermodynamic mixtures, the former being consistent with a steric effect control of the substituents and the latter by the electronic effect of the ring oxygen. Seven sugar aldehydes with different D-pyranosidic (2,3,4,6-tetra-O-benzyl-gluco, -galacto, and -manno, 2-azido-3,4,6-tri-O-benzyl-2-deoxy-galacto) and D-furanosidic moieties (5-O-benzyl-2,3-isopropylidene-ribo; 2,3,5-tri-O-benzyl-ribo; 2,3:5,6-di-O-isopropylidene-manno) were prepared in 52-65% isolated overall yield from the corresponding lactone.
• Thiazole as Leaving Group. Thermal Elimination from Thiazolylketoses
  作者：Alessandro Dondoni、Alberto Marra

  DOI：10.3987/com-98-8154

  日期：——

  Heating thiazolylketofuranoses and -ketopyranoses in refluxing toluene results in the elimination of thiazole and formation of the corresponding sugar lactones in nearly quantitative yield. The same reaction does not occur with 1-O-acetyl and 1-O-trimethylsilyl derivatives. Also model furyl- and thienylketofuranoses and various thiazolyl alcohols proved to be stable under the above thermolysis conditions. A possible mechanism of the observed thermolysis of thiazolylketoses involves the thiazolium 2-ylide as the actual leaving group.