2,3,4,6-Tetra-O-benzyl-1-(2-thiazolyl)-α-D-galactopyranose | 160701-76-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,6-Tetra-O-benzyl-1-(2-thiazolyl)-α-D-galactopyranose
• 英文别名: (2R,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)-2-(1,3-thiazol-2-yl)oxan-2-ol
• CAS: 160701-76-8
• 化学式: C₃₇H₃₇NO₆S
• 分子量: 623.77
• InChiKey: GUQAWDZPBOBRNR-YJOVGYIHSA-N

物化性质

• 沸点：
  746.070±60.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.290±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  2,3,4,6-Tetra-O-benzyl-1-(2-thiazolyl)-α-D-galactopyranose 在 4 A molecular sieve 、 三氟化硼乙醚 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.08h， 生成 4-Pentenyl 3,4,5,7-tetra-O-benzyl-1-O-[2,3,4,6-tetra-O-benzyl-1-C-(2-thiazolyl)-α-D-galactopyranosyl]-α-D-galacto-heptulopyranoside
  参考文献：
  名称：

  酮糖迭代糖苷化化学合成线性和环状非天然低聚糖

  摘要：

  描述了立体选择性合成 alpha-D-(2-->1)-连接的酮苷低聚物的有效方法的开发。该方法基于由两个关键步骤组成的迭代方案：a) 噻唑基酮基亚磷酸酯供体与羟甲基酮苷受体的偶联；b) 在所得低聚物的异头碳原子上引入羟甲基。为了突出其效率，该协议被用于通过 alpha-(2-->1) 连接到五聚体阶段的 D-galacto-2-heptulopyranose 低聚酮苷的组装。分离出的低聚物的产率范围从第一个循环的 48% 到第四个循环的 29%。在第一个循环中使用了戊烯基取代的羟甲基酮苷受体，所有衍生的低聚物在其还原端都含有戊烯基。该组被利用通过分子内糖苷化将线性低聚物转化为环状产物。X 射线晶体学证实源自线性三糖的主要产物是环三-(2-->1)-(α-D-galacto-2-heptulopyranosyl)。该化合物的结构基本上是带有三个吡喃半乳糖环的 [9] 冠 - 3 醚的结构，以

  DOI：

  10.1002/1521-3765(20010401)7:7<1371::aid-chem1371>3.0.co;2-j
• 作为产物：
  描述：

  2,3,4,6-四-O-苄基-D-吡喃半乳糖 在 正丁基锂 、 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.92h， 生成 2,3,4,6-Tetra-O-benzyl-1-(2-thiazolyl)-α-D-galactopyranose
  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

• 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.
• 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.
• Chemical Synthesis of Linear and Cyclic Unnatural Oligosaccharides by Iterative Glycosidation of Ketoses
  作者：Alessandro Dondoni、Alberto Marra、Marie-Christine Scherrmann、Valerio Bertolasi

  DOI：10.1002/1521-3765(20010401)7:7<1371::aid-chem1371>3.0.co;2-j

  日期：2001.4.1

  the isolated oligomers ranged from 48 % in the first cycle to 29% in the fourth cycle. Having employed a pentenyl-substituted hydroxymethylketoside acceptor in the first cycle, all the derived oligomers contained the pentenyl group at their reducing end. This group was exploited to transform the linear oligomers into cyclic products through intramolecular glycosidation. The major product derived from

  描述了立体选择性合成 alpha-D-(2-->1)-连接的酮苷低聚物的有效方法的开发。该方法基于由两个关键步骤组成的迭代方案：a) 噻唑基酮基亚磷酸酯供体与羟甲基酮苷受体的偶联；b) 在所得低聚物的异头碳原子上引入羟甲基。为了突出其效率，该协议被用于通过 alpha-(2-->1) 连接到五聚体阶段的 D-galacto-2-heptulopyranose 低聚酮苷的组装。分离出的低聚物的产率范围从第一个循环的 48% 到第四个循环的 29%。在第一个循环中使用了戊烯基取代的羟甲基酮苷受体，所有衍生的低聚物在其还原端都含有戊烯基。该组被利用通过分子内糖苷化将线性低聚物转化为环状产物。X 射线晶体学证实源自线性三糖的主要产物是环三-(2-->1)-(α-D-galacto-2-heptulopyranosyl)。该化合物的结构基本上是带有三个吡喃半乳糖环的 [9] 冠 - 3 醚的结构，以