Methyl 2-Deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside | 130729-66-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 2-Deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside
• 英文别名: (2R,3R,4R,6R)-2-[(1R)-1,2-dihydroxyethyl]-6-methoxy-6-(1,3-thiazol-2-yl)oxane-3,4-diol
• CAS: 130729-66-7
• 化学式: C₁₁H₁₇NO₆S
• 分子量: 291.325
• InChiKey: SPTDENSEPZBNGZ-UEWQFTGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.19
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  112.27
• 氢给体数：
  4.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  Methyl 2-Deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside 在 sodium hydroxide 、 对甲苯磺酸 、 silver nitrate 、 溶剂黄146 作用下， 以 四氢呋喃 、 水 、 丙酮 为溶剂， 反应 170.25h， 生成 3-deoxy-α-D-manno-oct-2-ulosonic acid
  参考文献：
  名称：

  A concise new route to 3-deoxy-d-manno-2-octulosonic acid (KDO) from D-arabinose and 2-acetylthiazole

  摘要：

  DOI：

  10.1016/s0040-4039(00)97663-9
• 作为产物：
  描述：

  (3R,4R,5R,6R)-4,5:6,7-Di-O-isopropylidene-3,4,5,6,7-pentahydroxy-1-(2-thiazolyl)-1-heptanone 在 Amberlyst 15 作用下， 以 甲醇 为溶剂， 反应 4.0h， 以30%的产率得到Methyl 2-Deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside
  参考文献：
  名称：

  丙酮酸衍生物的直接羟醛反应：合成 Ulosonic Acids 的催化尝试

  摘要：

  丙酮醛二甲基缩醛和 2-乙酰噻唑与糖醛的催化不对称羟醛反应被证明是合成 3-脱氧-2-ulosonic 酸的关键步骤。金属基手性 Trost 和 Shibasaki 催化剂可催化高效且立体选择性的丙酮酸醛醇反应。所提出的合成方法通过使用金属基手性催化剂直接活化 C3 丙酮酸等价物来模拟醛缩酶催化的反应，合成 2-keto-3-deoxy-D-glucosonic 酸和 3-deoxy-D-甘露糖-2-辛糖酸衍生物。

  DOI：

  10.1002/ejoc.201200325

文献信息

• Chemistry of the enolates of 2-acetylthiazole: aldol reactions with chiral aldehydes to give 3-deoxy aldos-2-uloses and 3-deoxy 2-ulosonic acids. A short total synthesis of 3-deoxy-D-manno-2-octulosonic acid (KDO)
  作者：Alessandro Dondoni、Pedro Merino

  DOI：10.1021/jo00018a017

  日期：1991.8

  The acetyl group of 2-acetylthiazole (2-ATT) was selectively metalated by treatment with lithium tert-butoxide (the lithium enolate was formed) or triethylamine/zinc chloride/trimethylsilyl chloride (the silyl enol ether was formed). The use of strong bases (LDA, TMP) resulted in substantial deprotonation of the thiazole ring. The lithium enolate of 2-ATT, formed under conditions of kinetic control, reacted with aliphatic and aromatic aldehydes to give the corresponding aldols (beta-hydroxyalkyl 2-thiazolyl ketones) in isolated yields of 51-65%. The reaction of the lithium enolate with chiral compounds, i.e., various alkoxy-substituted aldehydes and one amino aldehyde derivative, occurred with a high degree of anti diastereoselectivity (80-92%), an outcome that was in accord with the Felkin-Ahn model for asymmetric induction. Hemiketalization of the aldols that resulted from the reaction of the enolate with D-glyceraldehyde acetonide and 2-O-benzyl D-erythrose acetonide and subsequent liberation of the formyl group by hydrolytic cleavage of the thiazole ring afforded the corresponding aldosuloses. Oxidation converted these to ulosonic acids. The application of this three-carbon-chain elongation to D-arabinose diacetonide afforded the octulosonic acid KDO in 6.8% overall yield.