Methyl 3,4:6,7-Di-O-isopropylidene-2-deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside | 130703-05-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: Methyl 3,4:6,7-Di-O-isopropylidene-2-deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside
• 英文别名: 2-[(3aR,4R,6R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-methoxy-2,2-dimethyl-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-yl]-1,3-thiazole
• CAS: 130703-05-8
• 化学式: C₁₇H₂₅NO₆S
• 分子量: 371.455
• InChiKey: SZVZKSAFENIMGO-VRDFHVSKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  96.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Methyl 3,4:6,7-Di-O-isopropylidene-2-deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside 在 sodium tetrahydroborate 、 水 、 溶剂黄146 、 mercury dichloride 、 silver(l) oxide 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 反应 0.5h， 生成 3-deoxy-α-D-manno-oct-2-ulosonic acid
  参考文献：
  名称：

  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)

  摘要：

  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.

  DOI：

  10.1021/jo00018a017
• 作为产物：
  描述：

  Methyl 2-Deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside 、 2,2-二甲氧基丙烷 在 对甲苯磺酸 作用下， 以 丙酮 为溶剂， 以70%的产率得到Methyl 3,4:6,7-Di-O-isopropylidene-2-deoxy-1-(2-thiazolyl)-α-D-manno-heptopyranoside
  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

文献信息

• Efficacious modification of the procedure for the aldehyde release from 2-substituted thiazoles
  作者：Alessandro Dondoni、Alberto Marra、Daniela Perrone

  DOI：10.1021/jo00053a055

  日期：1993.1
• 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.
• A concise new route to 3-deoxy-d-manno-2-octulosonic acid (KDO) from D-arabinose and 2-acetylthiazole
  作者：Alessandro Dondoni、Giancarlo Fentin、Marco Fogagnolo、Pedro Merino

  DOI：10.1016/s0040-4039(00)97663-9

  日期：1990.1